DE2509414C3 - Coating compound for the production of light-sensitive layers of copy-out materials - Google Patents

Description

R ⁴

R- '

R ²

N NR ¹

(I)

R ⁴ R ^J

R ^s <} = - R ² (U)

contains, wherein X is an oxygen atom or an alkylene group, R and R _{1 are} each a hydrogen atom or an alkyl group, R _{2 is} an oxygen atom or an imino group, R ₃ and R _{4 are} each a hydroxyl or amino group, where Rj and / or R _{4 is} a Must be hydroxyl group. and R _{5 is} an optionally substituted aryl group or a group of the formula

O O

R "R ⁷

(HI)

40

wherein R "and R ₇ is each an alkyl group.

2. Coating composition according to claim 1, characterized in that it acts as a stabilizer 5,6 - isopropylidene ascorbic acid, 2 - hydroxy-3 - piperidino - 5 - methylcyclopent - 2 - en - 1 - one, 3,4-dihydiroxy-5-phenyl-2,5-dihydro-2-furanone. 5 - imino - .3,4 - dihydroxy - 2 - phenyl - 2,5 - dihydrofuran, 2-isopropyl-4,5,6-trihydroxypyrimidine or 4,5-dihydroxy-1-methyl-2-propyl-6-pyrimidone contains.

3. Coating composition according to claim l, characterized in that it is 2 to 25 percent by weight Stabilizer, based on the weight of the leuco dye (s). contains.

4. Coating Niasse according to claim 1. da- (> o characterized in that they are a polyester, a polyamide or a polyvinylacelal as a binder contains.

5. Photographisclves Auskopiennatena! with a lichienip- <> <applied to a layer support Linden layer made of a coating material according to Claims 1 to 4.

The Erfi.idling relates to a coating material for Production of light-sensitive layers of copy-out materials, the at least one leuco dye, a photo-oxidizing agent, a stabilizer and optionally contains an optionally photosensitive binder.

In special areas of photographic, ζ. Β. when using lithographic printing plates and Photoresist materials are known to provide a visual indication of exposure prior to operation development to be beneficial, especially when staged or repeated exposure of the recording material takes place and when the recording materials between exposure and development can be kept for a period of time or when a review is due to exposure image to be produced before development is desirable. To identify the exposure to make, is known to be the coating material used to produce the recording material an indicator dye added to the exposure of the radiation-sensitive recording material can either be copied or faded. Typical such exposure indicator dyes are z. B. photochromogenic dyes such as spirobenzopyrans, e.g. B. 3 ', 3'-dimethyl - 6 - nitro -Γ - phenylspiro [2 H -1] benzopyran-2,2'-indoline and 5'-methoxycarbonyl-8-methoxyl ', 3', 3 '- trimethyl - 6 - nitrospiro [2H - l] benzopyran-2,2'-indoline, also pH-sensitive dyes, e.g. B. Bis [4,4'-bis (dimethylamino) benzhydro] ether in Combination with certain activators, as well as cyanine dyes, as for example in the US-PS 36 19 94 are described in more detail.

It is also known, for example from Phot. May be. Eng., 5, 1961, pp. 98,103 and U.S. Patent 3,042,515, in the context of photographic processes using leuco dyes to the corresponding dyes to oxidize organic polyhalogen compounds or oxidizing agents. In a typical procedure of this type becomes a photographic material having a layer containing diphenylamine and carbon tetrabromide imagewise exposed to ultraviolet radiation. Because of the exposure the carbon tetrabromide is destroyed, with the decomposition products producing the diphenylamine oxidize a blue dye. From US-PS 36 15 568 are further recording materials known, in thnen the halogenated hydrocarbons are replaced by photooxidants that a have heteroeyclisches nitrogen atom which is substituted by an alkoxy or acyloxy radical.

It has been shown that from US-PS 36 15 568 known recording materials are superior to those of US Pat. No. 3,042,515 because they are compared to radiation other than UV radiation are sensitive, as can be seen from column I, lines 55 to 66 of U.S. Patent 36 15 568 results. However, it has been shown that the AuOeichnungsmaleriahen known from US-PS 36 15 568 are not lagerungsbestäiidig and that they are in the US-PS 30 42 * 515 in column K). / rush (-> 7 to stabilize column 1 1st line 4 described With the exception of the p-aminophenol, do not allow to stabilize. The latter connection ha! However the disadvantage that it is a skin remedy.

From US-PS 30 42 515 it is also known that the discoloration of leuco dyes due to the action of air or oxygen

avoid waiting for light and warmth, if the leuco dyes together with an organic one A reducing agent is used which has a benzene ring which is substituted by a hydroxyl group is provided there is at least one further hydroxyl group or amino group in another Ring position is present, such as. B. in the case of hydroquinone, catechol *, resorzinol, hydroxyhydroquinone and phloroglucinol, as well as in the case of Aminophenols, e.g. B. o-aminophenol and p-aminophenol.

It is also known / .. B. from US-PS 29 36 30S. that reductones due to the presence of enolic hydroxyl groups with respect to those present therein unsaturated bonds are strong reducing agents.

The object of the invention is the effective stabilization of photographic copy materials for the production usable coating compositions which contain at least one leuco dye. one Contain photo-oxidizing agents and optionally a binder.

The invention is based on the knowledge that the stated object can be achieved by using leuco dyes to incorporate certain reductones as stabilizers.

The invention relates to a coating compound for the production of light-sensitive layers of copy-out materials that contain at least one leuco dye, a photooxidant. a stabilizer and optionally a light-sensitive one Contains binder, which is characterized in that it is a compound as a stabilizer the formula

NR ¹

(in

contains, wherein X is an oxygen atom or an alkylene group, R and R ₁ each a hydrogen atom or an alkyl group, R ₂ an oxygen atom or an imino group, R, and R _{4 must} each be a hydroxyl group, and R ₅ an optionally substituted aryl group or a Group of formula

Wi) IiIi R ₁ , and R- icweils equal to an A! K_ \ Igruppi. is. The groups R and R 'on the one hand, and R ¹ and R ^a as well as R''and R on the other hand can have the same or different meanings

The addition of the reductones to an effective stabilization of the Bescliichtungsrr.asse can prior to use, ie, before application to a substrate and ¹ after application to a support, d. h achieve an effective stabilization of the produced drawing materials. The stabilizers used according to the specification protect the coating composition and recording material from discoloration and the occurrence of dark reaction products which lead to background discoloration of the recording / calibration materials produced from the coating compositions.

H-'t in the given formula II X denotes an alkylene radical, this preferably has one or two carbon atoms, that is, X preferably consists of a methylene or ethylene radical. The use of reductions of the formula 11, in which X is a methylene radical, has proven to be particularly advantageous. Have in the formula IR and R 'the meaning of alkyl radicals. so these preferably have 1 to 4 carbon atoms. ie. in this case, R and R ¹ preferably consist of methyl, ethyl, propyl or butyl radicals.

^{If R 3} and / or R ⁴ in the formula 11 have the meaning of amino radicals, then these amino radicals can consist of primary, secondary or tertiary amino radicals. In the case of tertiary amino radicals, the amino radical can consist of a cyclic radical, for example a piperidino radical.

In formula III, R ' ¹ and R ⁷ preferably represent alkyl radicals having 1 to 4 carbon atoms.

R "uml \ 1 ^Ί preferably have the same meaning. Particularly advantageous compounds are present when R ' ¹ and R ⁷ each represent a methyl radical.

^{If R 5} in formula II is an aryl radical, this preferably consists of an optionally substituted phenyl or naphthyl radical. If R ^{5 is} a substituted aryl radical, this can be substituted, for example, by alkyl radicals, preferably those having 1 to 10, in particular those having 1 to 5 carbon atoms, e.g. B. methyl-. Ethyl, propyl, butyl, pentyl, hexyl, heptyl. Octyk nonyl or decyl radicals or isomers thereof. Furthermore, the ^{aryl radical represented by R 5} can be substituted, for example, by carboxyl radicals und'oder Alkoxycarbonylrestc, for example Methoxycarbonvl-. Ethoxycarbonyl and / or propoxycarbonyl radicals.

As a particularly advantageous reductone for production coating compounds according to the invention and copying materials according to the invention have become For example, it has been found that: 5,6-isopropylidenaseorbic acid; 2-Hydroxy-i-piperidino-S-methyl-cyclopent-2-en-1 -one: 3,4-dihydroxy-5-5-phenyl-2,5-dihydro-2-funinone: 5-imino-3,4-dihydroxy-2-phenyl-2,5-dihydrofuran; 2 - isopropyl - 4,5,6 - trihydroxypyrimidine and 4.5 ■ · dihydroxy-1-methyl-1-propyl-d-pyrimidone.

Preferably the reductone is in one concentration from about 2 to about 25 fvw .- 'O. related to diis weight.! cn or the 1 euk'-iarbsiofle. before. When especially useful! sn.h has a reducton concentration. based on the choice of the l.eukoiibstolTe. about

until

a 20 (iew -'Ό proved.

/ ', Ii !! ersieilung ctTmdungsgcma'Lv] BeschuitUingsiiiassen s. w ic a fmdgemüßei more photographic Auskopienii.iterialien can be the usual, well-known volumetric elements and PhiMcioxjdaiionsmitlel used

such as those described in US Pat 36 15 568 are known. Examples of suitable lecoric dyes are the leuco forms of the following color UoITk let:

a) Aminotriary! methane.

b) aminoxanthenes,

c) aminolhioxanthenes,

d) Amino-9, 10-dihydroaeridines.

e) aminophenoxazines,

f) amiiiophenothiazine,

g) aniinodihydrophenazine,
h) aminodiphenyl met haue,
i) Leukoindaiiiine.
j) aniinohydrocinnamic acids

(Cyanoethane, lcukomethine),
k) hydrazines,

1) Leueo-indogoid-color slol'fe,
m) Amino-l ^ -dihydroanthraquinone and
n) phenethylaniline.

It is preferred to use photo-oxidizing agents which are inert until they are actinic to the action Exposure to radiation such as visible, ultraviolet and infrared radiation as well as X-rays, electron beams and the like, depending on the structure of the photo-oxidizing agents these have different peak sensitivities within the spectrum. As a result, the choice becomes of the photooxidation agent used in the individual case on the type of actinic acid to be used Radiation affects. Upon exposure, the photo-oxidizing agent forms an oxidizing agent, which converted the leuco dye into a dye.

Typical for the production of a coating composition according to the invention and one according to the invention Photooxidizing agents suitable for photocopier painting are known from US Pat. No. 3,615,568. Characteristic for these compounds is a heterocyclic nitrogen atom, which is replaced by an alkoxy or aryloxy radical is substituted.

Photo-oxidizing agents of this type can be expressed, for example, by the following structural formulas reproduce:

Z-.

- R "

OR *

-R ¹

OR "

wherein R * denotes an optionally substituted one <«Alkyl radical or an aralkyl radical or an acy read !. R '' a methane bond with a heterocyclic Core of the odci type known from the cyanine dye or an optionally substituted alkyl or aryl radical or a hydrogen atom or emeu acyl <> · Or anilinovinylresi or a given alkali substituted Styrofoam. There is no link with a terminal, historical core ties Meroeyaninfarbstol'fen known type or emeu optionally substituted Ailylidenrcsl, Z the for the completion of a 5- or 6-membered heterocyclic nucleus required atoms and X a S acid anion.

For further details, reference is made to US-PS 15 56S.

The coating compositions and recording materials according to the invention can be prepared according to customary methods ίο establish known methods, d. H. for example by mixing a dispersion or solution of the Leukofarbslofles with one of the photooxidation agents described! and one of the specified stabilizers and optionally a binder, woris applied to the mass on a layer support or used for impregnation! can be or possibly also for the production of self-supporting layers.

A wide variety of binders can be used to produce coating compounds ».

with the help of which leuco dye, photo-oxidizing agent and stabilizer on the carrier or substrate for Adhesion can be brought. The binder can also serve to add to the coating masses thicken if so desired.

Inert as well as light-sensitive materials can be used to produce the coating compositions and copier materials Binders are used.

Examples of suitable inert binders are:
10

Styrene-butadiene copolymers.

Silicone resins,

Styrene alkyd resins,

Silicone alkyd resin c.

Soy alkyd resins.

Polyvinyl chloride.

Polyvinylidene chloride.

Vinylidene chloride-aerylnitrile-miseh polymers.

Polyvinyl acetate.

Vinyl acetate-vinyl chloride mixed polymers.

Polyvinyl acetyls,

z. B. polyvinyl butyral,

Polyacrylic acid and polymethacrylic acid ester.

z. B. Polymethyl methacrylate.

Poly-n-butyl methacrylate c.

Polyisobutylinethacrylate ti. like ..

Polystyrene,

nitrated polystyrenes,

Polymethylstyrene,

Isobutylene polymers.

Polyester, e.g. B. Poly (ethylene alkaryloxyalkylene

terephthalate).
Phenol formaldehyde stocks.
Ketone resins,
Polyamides.
Polycarbonates.
Polythiocarbonates.

Poly (ethylene glycol-eo-bis-hydroxyethoxyphenylpiopanterephthalate).

Mixed polymer from Viny Ihaloacrylics and Yinylacciaten. /, H Polyivinyl-m-hromben / oateo- \ inylacetatl.
Ethyl cellulose.
Polyvinyl alcohol.
(. ellulose acetal.
Cellulose nitrate,
chloiated
(ielatine u dul.

m ^ ^m

Such binders are known from a large number of materials. Suitable styrene-alkyd resins can be prepared, for example, by processes such as those known from US Pat. No. 2,36,019 and 2,255,423. Suitable binders are also commercially available, for example under the trade names Viicl I ¹ U-IOI. Cymnc. Piccopale 100. Saran I -220. 1.exane 105 and l.exane 145. Paraffin and mineral waxes, for example, can also be used as binders.

Polyvinyl acetate, Polyamides as well as polyester are used.

Particularly advantageous binders for the production of coating compositions and printouts according to the invention are further z. B. in DT-OS 24 42 558 described.

Accordingly, for the production of the coating materials and recording materials can be used in an advantageous manner Qucrnctzbarc condensation polymers with an inherent viscosity of at least 0.20, 98 to 55 mol% of the acid components of which are made up of recurring, cross-linked bars Units (I) of a dicarboxylic acid with at least one non-laromatic. ethylenically unsaturated Bond and the remaining acid component consists of 2 to 45 mol% of recurring units (11) consists, which are characterized by a water-solubilizing disulfonamido radical with a monovalent cation on the amido nitrogen alom.

Such copolyesters can be produced by condensation of one or more polyhydric Alcohols with at least two carboxylic acids, each of which has at least two condensation centers having. At least one of the two carboxylic acids contains at least one non-aromatic, Ethylenically unsaturated radical, while at least one or the other carboxylic acid has a solubilizing sulfonate residue. The non-aromatic, ethylenically unsaturated residue looks for a carbon-carbon double bond in both an aliphatic and an acyclic residue. / 11 is to be observed. that if necessary the donkey residues can be replaced by amido residues, at least partially. This can be easily achieved by making the copolyester in the presence of amino alcohols, diamines or amino acids. The carboxylic acids can be separated in their free acid form or in the form of an unclear derivative. /. Am Form of an anhydride, a short-chain alkyl lithium (Do not use any acid halide.

According to a particularly advantageous embodiment of the invention, the components are described Type used whose recurring units (I) from photosensitive units of the from US-PS 30 30 2OS of known type exist. Such repeating units have at least two condensers sationszciilrcn on, with at least one condensate sationszenlium from a resl of the following formula ii title:

CII C

(Al

which is bound directly to an animal core.

For example, R ' ¹ ' stands for a llydro \ yltesl. in

in which case the compound is a free acid or an oxygen atom bond. in which case the compound is an acid anhydride, or a halogen atom, in which case the compound is in the form of an acid halide, or R ' ⁴ is an alkoxy radical. in which case the connection is in the f'oi m of a listener.

The repeating units (I) with the rest (Al are preferably formed from cinnamic acid or its derivatives. Such connections can be expressed quite, generally, by the following formula:

(H - CH-CR ¹

where R ^{14 has} the meaning already given and R ^IS indicates that the benzene ring can be replaced by one or more alkyl, aryl, aralkyl, alkoxy, nitro, amino, acrylic or carboxy radicals or halogen radicals

2s atoms can be substituted, the substitution is such that at least one condensation center is created.

In order to increase the concentration of light-sensitive residues (A), a particularly advantageous

ίο embodiment of the invention R ¹⁵ can be selected such that the benzene of the formula (B) is substituted by at least one further radical of the formula (A).

A particularly advantageous connection for the

AS Formation of recurring units (I) is p-phenylenediacrylic acid together with its derivatives. Other suitable compounds for the preparation of the copolyesters are described in the already cited US-PS 30 30 2w.

. | o Further connections that lead to education again recurring healing (I) can be used from IIS-PS 37 02 765 and 36 22 320 known Aul these two patents is expressly referenced.

According to a further, particularly advantageous embodiment of the invention, de Hardware and Auskopiei materials Bin deniiltel used with recurring healing (II which are produced from dicarboxylic acids of the following formula:

Il

CR ' YR ^M

Il ο

R ¹ "CH CIl C

where R "has the conditions already given R '"for an alkylidene, aralkylidene or helern cyclic radical or a derivative thereof.

Examples of the acids which the given generalgi correspond to my formula ((Ί and (lic see as special

/ OH (!, 1Ι. / ΪΗ

This is advantageous for the production of coating compounds and copy-out materials proved to be the invention are for example cinnamylidene malonic acid: 2-butene vliden malonic acid; 3-penienylidene malonic acid: o-Nilroeiiinam> lidenmalonic acid: Naph-ιhy tally lidcnmalonic acid; 2-furfurylidene ethylidene malonic acid; N-Melhvlp \ ridylidcn-2-etherealide malonic acid; N-methyl-ehinoliden-2-ethylidenemalonic acid: N-MelhylluMi / .oihiazolyliden-2-ethelidenmalonic acid and the like as well as functional derivatives of these acids. Such acids are for example closer in the US-PS 36 74 745 retained.

According to a further, particularly advantageous embodiment According to the invention, binders are used for the production of the coating compounds and print-out materials with repeating units (I I used, derived from the muconic acid or a funklionellen Derivative of the following general formula can be generated:

C)

R ¹⁴ - C - C CH - CH - C - C - R ¹⁴ (D)
R ¹⁷ R ¹⁷

Meaning, or one

Here, R ^{14 has} the value already indicated
and R 'stein for a hydrogen aiom
Methyl radical.

Examples of suitable compounds of the formula (D) are trans, traus-muconic acid; eis.trans-muconic acid; cis.cis-muconic acid; n. u -cis.l ran s- dimethyl muconic acid and ci.ii'-eis.cis-dimethylmuconic acid. These and other mucosal ulcers. which can be used to generate the recurring units (1) are described in more detail, for example, in 'JS-PS 36 15 434.

According to a further, particularly advantageous embodiment of the invention, the coating compounds graze and copy-out materials using binders of the type described produced in which the recurring healing! I) from unsaturated carbocyclic dicarboxylic acids or their derivatives. Such connections can be through the following. ' general formula ken η / eich new;

C)
R ¹ 'CC

C C R generate d. H. Connections that result from the following show the general formula:

O C)

RCCR ¹⁴

R ¹

wherein R ^{14 has} the meaning already given and R ^{1S is} a hydrogen atom or an alkylresl with I to

is 12 carbon atoms, and / was a straight chain or ver / whelkeltiger alkylresl or a cyclic one Alkyl radical. i.e., for example, a methyl. Ethyl, Propyk Isopropyk Butyl, l.-Bulvl-. Aiml, neopenlyl or cyclohexyl radical or but a mono-

: o or polynuclear arylresi. z. B. a possibly substituted phenyl or naphilene residue. The alkyl and aryl radicals can be substituted by substituents which do not interfere with the condensation reaction, for example by halogen atoms and or Nitro, aryl, alkoxy and / or aryloxy radicals.

The carbonyl residues are located in meta-oil parallels to each other, preferably in the para position to each other on the cyanohexadiene nucleus.

Particularly advantageous cyclohexadiene dicaibon

} o acids are, for example, 1,3-C> clohexadiene-1,4-dicaibonic acid. I, 3-C>clohexadiene-1,3-ilieai'boxylic acid. !,. Vcyclohexadiene-l ^ -dicarboxylic acid. 1,5-cyclohexadiene-1,4-dicarboxylic acid, 1.5-C \\ clohexadiene-1,3-dicarboxylic acid and alkylated and aiylated derivatives

is of these acids. Such acids as well as t'ire functional Derivatives are described in more detail in BE-PS 7 54 S ') 2 to which reference is hereby made.

The / wide repeating units (II). you exist to the! transforming Copolymcrei

. | i> to make soluble in aqueous alkaline solutions before cross-linking takes place, aroma table dicarboxylic acids or their derivatives, including those with a disnll'on amidoresl, d. H. a resi of the formula

SO, N SO,

in which the amidoslicksiol'falom as / nsäl / liclu'i Substiluenlen a solubilizing Kaiion aiil'weisi Such aromatic dicaibonic acids are perfectly acceptable those of the following formula:

where R "ilie already has a right degree of division and /." for the Alome sees, ilie / ui VeivollsliituliiMin.r of an iini'csäliijMcn, i.'ej'ebeiu'nl'all a Hnickenhindinii ¹ showing, carbocyclischon none mti in the Rejiel d up to 7 carbon atoms eiloiderlich the eai'ltocu'are none can thereby be cyebciieiilalls subsliluierl. Particularly favorable acids of this type are the 4-Cyelolu'U'n-I .. ^ ¹ clicarbosylsäuie, the S-Nonbonu'ii 2.3 dicaibons; iuie as well as the llexa chloro - 5 | ?.: 2: I | - bicyclolu'plen - 2,3 - dicai bonsiiure.Deiarlige Siiiiren are described in detail in the CA-PS 8 24O ¹ Hi, which is hereby referred to. The recurring units (I) m'l residues of the formula ( Ii) can further, starting from the CvcloheMiilieiHlicaibonsiiiire and its derivatives,

<■ 'Y Q, "

u :,

worm R ¹ ″ has the meaning already given in in which also denote in and ft numbers, the sum of which is l'Jeich I; Q is a remainder of one of the following formulas

S Y

(G-I)

(.) 'a remainder of the foaling formula:

O M O

SNS V-

I ₁ Μ

'<Ii

O I)

((1-2)

Y is an aromatic radical, for example an arylenresl, e.g. B. a phenylene or naphthylene resin or an arylidine structure. z. B. a Phcnenylrest. C ₁₁ H ,, or a naphthylidyne radical. C ₁₁₁ H ₅ and the like. Y 'is an alkyl or aromatic radical, for example an aryl, alkaryl or aralkyl radical, in which each of the alkyl radicals preferably has 1 to 12 and in particular I to (S carbon atoms, and M a solubilizing cation , preferably a monovalent valent cation, e.g. an alkali metal or ammonium cation.: o

Compounds which are preferably used to generate recurring units (II). are:

3,3 '- [(Sodium imino) disuironyl] dibenzocic acid. js 3,3 '- [(Potassium-imino) disulfonyl] dibcnzoic acid.

3,3 '- [(lithium-imino) disulfonyi] -dibenzoic acid, 4,4' - [(lithium-imino) disulfonyl] -dibenzocic acid c.

4,4 '- [(Sodium-imino) disulfonyl] dibenzoic acid.

4,4'-r (potassium-imino) disulfonj ⁱ l] dibenzocic acid c. ^ o 3,4 '- [(lithium-imino) disulfonyl] -d! benzoic acid, 3,4' - [(sodium-imino) disulfonyn-dibenzoic acid.

5- [4-Chlornaphlh-l-ylsulfonyl- (sodium imino) -

sulfonyl] isophthalic acid,
4,4'- | (potassium imino) disulfonyl] dinaphthoe- is

acid,
5- [p-Tolvl-sulfonyl- (potassium-imino) -sulfonvl | -

isophthalic acid,
4- | p-Tolyl-sulfonyl (sodium-imino) -sulfonyl | -

I "S-naphthalenedicarhonic acid,. | O

5- | n-Ilexylsulfonyl- (lithium-imino) -sulfonyl | -

isophthalic acid,
2- | Phenylsulfonyl- (potassium-imino) -sullbnyl] -

lerephthalic acid and

functional derivatives thereof. . | s

These and other dicarboxylic acids, which are used to generate the repeating units (I D of these Coulensation copolymers are suitable, we will find out more for example in IIS-PS 35 46 180 described. so

In a particularly advantageous manner, the condensation ^{copolymers used are composed of 1} > H to 55 mol% of recurring units (I) and 2 to 45 mol% of recurring units (II), these mol percentages being based on the ss total amount of existing SHureeinheiteu relate. In especially advantageous manner, the (are '! "polymers to ⁽⁾ from 7 to 85 mol% of recurring Hinheilen (I) constructed and 3 to 15 mol ^1' 'of the recurring units (II) , based on the total amount of acid units present.

In addition to recurring dicarboxylic acid units (I) and (II), which bring about animal crosslinking or solubility of the polymers, these condensation copolymers can also have recurring units (III). According to a particularly advantageous embodiment of the invention, these recurring units are produced from dicarboxylic acids or their derivatives; which
let us see the following formula again:

R '

CD -CR ¹⁴

through the

(H)

where R ' ^{4 has} the meaning already given and 1) is a divalent hydrocarbon residue.

Preferably D consists of an arylene or Alkylene radical. The repeating units (111) are preferably composed of one or more carboxylic acids or their functional derivatives having 3 to 20 carbon atoms. Particularly advantageous aromatic dicarboxylic acids for generating the recurring units (III) are phthalic acids, z. B. phthalic acid. Isophthalic acid and terephthalic acid. Examples of suitable aliphatic dicarboxylic acids are: malonic, succinic, glutaric, adipic, pimc-Hn, suberic, azelaic and sebacic acids and others higher homologous dicarboxylic acids. Since the repeating units (III) neither for solubilization nor contribute to the crosslinking of the condensation copolymers, they are only if appropriate before. If such units are present, they can account for up to 43 mol% of the copolymers, based on the total amount of acids. Preferably, the repeating units (111) make not more than 25 mol% of the copolymer, based on the total acid units.

The repeating units (1), (II) and (III) can in the condensation copolymers by repeating units (IV) with one another be connected that are derived from bifunctional compounds that lead to a condensation with a carboxylic acid or a functional derivative thereof. Advantageously, they lead the repeating units (IV) from one or more diols of the following formula:

HO R ¹

where R '"is a divalent organic resin with preferably 2 to 12 carbon atoms composed of hydrogen and carbon, slol talomine and optionally ether oxygen atoms. In a particularly advantageous manner, R ¹ " consists of a hydrocarbon radical, ζ. Β a straight or branched alkylene glycol. z. B. an ethylene, Triinethylene or Neo pentylenrest or a Cycloalkylenrcst, z. B. a cyclohexylene radical or a Cycloalkylenbisalkylcnicst, /., H. a I ^ -Cyelohexylcndimelhyleniesl or an Arylenresl, / .. H. a phenylene radical, or a hydrocarbon - oxy - hydrocarbon radical, z. H. an alkylene-oxy-alkylene radical or an alkylene-oxy-cycloalkylene-oxy-alkylene radical ti. like

Examples of suitable diols that can be used for the preparation Coilensation copolymers don't really exist can are:

Ethylene glycol.
Diethylene glycol.
1,3-pi'opaiuiiol,
1,4-butaudiol,
1,5-pentanediol.
1.6-1 lexanediol,
1.7-1 leplandiol,
1,8-octanediol,

1.9 nonanediol.

I.IO-decanediol.

I.I 2-dodecanediol.

Neopenlyl glycol.

I ^ -Cyclohexanedimethanol and

l ^ -Hisl / i-hydroxyalhoxyl-cxclohexane.

If necessary, corresponding diamines can be added In place of the diols or in place of a part of the diols for the curing of the condensation mixture polymers be used. Mixtures of one or more diols or one or more diols can also be used Diamines are used to produce the condensation mixed polymer.

On a molar basis, the recurring units (IV) correspond to the sum of the number of recurring healing (1). (11) and (111). In the In practice, it has often proven advantageous to use an excess of up to about 10 mol% of the To use reaction components which lead to the formation of the repeating units (IV). The condensation copolymers which can be used according to the invention can be prepared in accordance with customary methods known methods take place, for example by such methods as those already cited in Palentcripts are described. In a typical way the condensation mixed polymers or Condensation copolymers by mixing the reaction components in the presence of a catalyst, for example bulyl titanate. Titanium oxopropoxide. Antimony oxide. Strontium oxide or / in acetate manufactured. It has proven to be an advantage if the mixed condensation polymers have an inherent viscosity from 0.2 to 1.0, preferably from 0.3 to 0.S exhibit.

Usual known solvents can be used for the production of the coating compounds which are inert towards the l.euco-l'arbsloffen and ilem or the reductions, the binding agent and the photo-oxidizing agent (ie suitable solvents which are used for the production of the Ingredients that can be used are amides. /. H. formamide; N, N-dimethylformamide; N, N-dimethylacetamide; also alcohols. E.g. methanol; ethanol; 1-propanol: 2-propanol: 2-propanol; Bulanol; also glycols, for example acetone and 2-bulanone; also lists. /.M. Ethylacelal and Älhylben / oal; distant ether. /.IJ. Tetrahydrofuran and dioxane; finally, chlorinated aliphatic hydrocarbons. /. IJ. Methylene chloride, ethylene chloride and dichloro-alcohol as well as fine aromatic hydrocarbons. /. H. Benzene and toluene and other common solvents, / U. Dimethyl sulfide; o-Dichlorobenzene: Dieyanoeyelobutane: I-methyl 2-oxohexamclhylenimiii and mixtures of solvents.

Beneficial results were obtained when the or the 1 euu> farbsloffc and the Photooxidalions Initlel in a ratio of about 10: 1 can be mixed with each other up to 1:10, a special one an advantageous mixing ratio is from 2: 1 to 1: 2, If a binding agent is used, it is preferably used in amounts of elwn () ,? up to 10 (.icw. parts per Gewiehlslcil i'iis LcucofaibstolT h / w lcucolaibslelten iiiul use Pholooxidalionsnüllel. The Total weight or combined (such as from icico dye and Pholooxidalionsmiltel in du Besehich lungsinasse makes about 1 to ')') wt .- 'tier Ueschichtimgsmasse (without I ostngsniillel) from, In be

in a special way hegi -.l.is weight ratio from 1 eucofarbsiofl and Pholooxiilalionsmiitel in the coating unit inline I ösimgsmitiell sth, ι Γ to elwa N> (iew .- "u.

Preferably, the Besehichluiigsmassen graze m such layers applied after the death a Stäikc \ on elwa 0.05 to 10.OMikion oilei point out. In the I all lithographic printing plates the thickness is preferably 0.1 to 5.0 microns.

The coating compositions can be applied to carrier elements in various ways, for example by spraying or brushing or rolling or by coating with a coating funnel. Furthermore, the coating compounds can be immersed or impregnation of the material to be coated can be applied to this or by flowing on on the surface. The coated or impregnated materials or elements can then be dried at room temperature under vacuum or at elevated temperature.

Graze with copy-out materials or elements produced in the manner described If actinic radiation is exposed, direct images are produced on the carrier. The exposure can take place according to the Kontaktkopicrverfahrcn, by projection by means of ones, by reflex or bileflex methodes. using a standard template to be mapped.

The usual known ones can be used as carrying materials Carrier materials are used, provided that they are not chemically associated with components of the coating compound react. This means that the layer support materials can consist of ilen customary known fibrous shoe carrier materials, for example from paper, from paper coated with a polyolefin, for example one with polyethylene oiler polypropylene coated paper, parchment oiler cloth or made from a sheet or a l'olie a MelaH./, IJ. made of aluminium. Copper, magnesium or zinc, or from (! read or a C! read that with is coated with a metal, for example with a (hi om- ('In omlegiei ling-, phthal-, silver-, (iold- or Platinum layer or from a layer support made of a synthetic polish, such as a Pohalk> laci \ lat. / H Polvnielhyhnelhaciylal odei a polyester. /. B. Polyälhylentcrephlhalat or a Pohvinylacetat or a polyamide. / B based on hexamethylenediamine and adipic acid or from a cellulose ester. /.H. Cellulose nitrate. CeIIu Loseacetat, Celluloscaeelatpropional or Cellulose · acelatbulyrat,

For the production of printing plates, in particular lithographic printing plates, substrates made of zinc-coated aluminum, roughened aluminum, copper and specially produced metal and paper layers in small foils made of cellulose esters, which are hydrolyzed on their upper side, and also substrates are suitable; polymeric substances, such as polyolefins. Polyesters and polyamides,

Before the application of the layer supports, the radiation-sensitive layer, Hall or / wipe layers can be applied. /. B. Layers on the copolymers !? made of vinylidene chloride and acrylic mono rivets, for example acrylonitrile. Methyl acrylate and the like, as well as unsaturated dicarbohydrates. /, I). ilaconic acid, distant ¹

■ J ''

15 16

from carboxymethyl cellulose, gelatin, polyacrylic, for example another antifoam agent and / or

amides and other polymeric substances. have a so-called anli-blinding agent, d. H.

Is deposited districts under load and improvement is made of a colored polymer layer containing the s of Einfärbwiderstandsfähigkeit: substrate also a olcophiles means preferably comprise in the image filter or antihalation layer ^- Optionally, can de.
radiation used for exposure is absorbed, which is recorded with the developer after this has passed through the radiation-sensitive material, then in a conventionally known manner the layer can be processed in order to avoid undesired reflection. So, for example, can be avoided from the substrate. If, for exposure printing plates, the hardening of the recording material is made using ultraviolet radiation, the effect of a desensitizing etchant, for example, light exposure has to be used. If the developed radiation-sensitive layer forms a resist layer from a polymeric binder of the sensitive layer, then the written-on type with a yellow dye as a drawing material can prove advantageous in a conventionally known manner. treated with an acidic or basic etchant and

The exposed, radiation-sensitive recordings are placed in a plating bath,

The following examples are intended to further illustrate the invention

Have photo-crosslinkable polymers, can be exemplified in.

Licher known way to be developed, namely. .

by treating the radiation-sensitive example 1

Layer with a solution (hereinafter as a developer 20 using the antioxidant in a

referred to), which the unexposed areas of the copy-out coating compound with an inert

radiation-sensitive layer selectively dissolves. The binders.

Treatment of the exposed recording material A. First, a light-sensitive coating

with the developer, for example, this means that processing material from the grain sizes specified below

take place so that the exposed material is made with the component:

winder is wiped off or that the material ^,. Γ,

is immersed in the developer or that the ent- ™ Γ ^ ^, T ™ \ ' ^recently

winder is allowed to flow over the material. 80.7% by weight of vinybutyral groups,

Typically the developer consists of a l? -? ™ '»? Y ^{'ny alkohoI} g ^{ru en} PP ^and _n "

aqueous alkaline solution with «" cm pH value y, ΑΐΑβΕ- '''*

from about 9 to 14. The developer can be, 1 1 ir, 1 1 λ \, ·,

ju-j u ι ·· ι- u u 11 ι- 1. w u p-toluenesulfonate (as copy

by soluble inorganic alkaline compounds Γ ,, ·. Q ^ ₁₁

fertilizers are caused, for example, by Tris (N, N-dipropylaminophenyl) - "

Use of alkali metal hydroxides, Phos- ^ _{o J _die Z _rer leuco dye) 0.2 a
phates, sulfates, silicates and carbonates or 35. ₍ 180 0 ml
Combinations of these. As an alternative or in combination with such inorganic alkaline compounds, basic, soluble, organic preparation of a solution can be used after a short time when the individual components are mixed to form bonds, e. B. amines, for example span a discoloration of the mixture.
wise triethanolamine, diethylenamine and diethyl 40 To a 10 ml portion of the coating mass aminoethanol. 1 mg of the reductone S.o-isopropylideneacoibine

The developer advantageously contains added acid. The resulting solution was in a Solvent system brought a bottle with a capacity of 25 ml, which can be mixed with one another, and 24 hours mix of water and alcohol. The relationship of long stirred. It turns out that the reductone in Water to alcohol can be very different. 45 effective way of further discoloration of the leg Typically, the solvent mixture is prevented from stratification.

20 to 80% by volume of water and 80 to B. The procedure described under A was repeated 5 times

20% by volume from alcohol. Repeated in a particularly advantageous manner, each with a different re-

The water content is around 40 to 60% by volume, ducton. In each case there was 1.0 mg of reductone

based on the total volume, with the remainder of the 50 instead of S.ö-Isopropylidenascorbic acid according to

Solvent system essentially or entirely from A used. With the tested reductones acted

Alcohol exists. To produce the developer it is:

various alcohols or alcohol ₍₁₎ ^ hydroxy .Vpiperidino-S-methyl-cyclopent-

combinations are used, which the strah- "» -en-l-on

lungs-sensitive layer during development 5? _η 3 4_Dihydroxy-5-pheny! -2 5-dihydro-

Process not chemically disadvantageously an- Vf _ura non

grab and the with water in the specified _{ver (3)} ^ mJno ^ .djhydroxv ^^ henyl - ^ - dihydro-

ratios are miscible. Examples of suitable furin

Alcohols are glycerine, benzyl alcohol 2-phenoxy-1-isopropvMÄfvtrihydroxypvnmidin and

ethanol. I.2-Propandio .sec.-Butylalkoholsow.e Ether. <* _{4 5} . _Dihydn , _xv , _{I. me} , hvl-2-propvl-6-pvrimidon.

derived from alkylene glycols, e.g. B. Dihydroxy- ""

polyalkylene oxides), for example dihydroxypoly- It was found that each of the reductonc tested

(ethyl oxide) and dihydroxypoly (propylene oxide). a further discoloration of the coating material

If necessary, the developer can prevent other sam.

Contain customary additives, for example dyes <> 5 C. The method described under A was still

and / or pigments. If the developer is repeated 11 times, but this time the following

developing the image of a lithographic print- the specified antioxidant of the booth

nlatle is used, it can advantageously be used in amounts of 1 mg.

instead of 5,6-isopropylidenaseorbic acid, which use Λ in the case of the test series! would. It was the antioxidant tested uiii:

Hin Ami, mni, .n, ι
I ') I lydnSon

While stirring the Mischi'ny, the pressure in the

Gradually reduce the reaction vessel to 0.05 mm Hg.

that at which pressure the reaction mixture was stirred for 40 minutes. The distillate became

^s ■ "<^» two dry ice-acetone traps.

(6) ni-dimethylaminophenol,

(7) triphenylstibine,
(K) phloroglucinol,

(')) N-methyldiphenylamine,

(10) urea,

(11) llexamethylene tetrainin.

Evidence.that.of the.e.et.An.ioxida.ionics only p-aminophenol a further discoloration effectively prevented. The disadvantage of using p-aminophenol, however, is that this is a is a strong skin stimulant. "

Example 2

Use of Rcduktonen in a AuskopierlU-layering compound with a photosensitive binder.

A. Manufacture of polyesters from Dtathy -

p-phenvle, idiacrvla..Dimethyl-3..V-r (sodium immo) -d.sulfonvlldiben / oatund l, 4-bis - (/ i-hvdroxväthoxv) -

¹ ti-

eyeionexan

liin photo- or light-crosslinkable polyester was made as follows:

A 200 ml condensation flask was filled in the following order: 0.007 mol of dimethyl-3, .V - [(tiatriuniimino) disulfonyl] -dibeii / oat.0.CW3 mol of diethyl p-phenylene diacrylate and 0.17 mol of 1.4- ( ₍ i -Hydroxyethoxy) cyelohexane.A side arm of the flask was closed with a cork through which a glass tube was inserted into the flask so that nitrogen could be passed through the reaction mixture during the first stage of the heating process -Column attached, for the purpose of refluxing the higher-boiling components of the reaction mixture during the first phase of heating with distillation of the alcohols obtained. The contents of the flask were melted by placing the flask in a silicone oil bath at a temperature of 235 ° C Two drops ('· ,,, ml) of titanium isopropoxide were added to the melt, whereupon the contents of the flask were heated to the return temperature for 4 hours rde. This then became the Vigreux column. the inert gas Einleitungsröhrchcn and the cork removed. whereupon the side arm of the piston was connected to a vacuum star. which was connected in series with two dry ice Vcton cases. The reaction mixture was then mixed with a stainless steel stirrer. which became ilv'i-.ii.hkM by means of a vacuum seal

^{On dicsc wcise was}

^{amber furbenes}

a. non-sensitive see Beschich ^{dil h}

Polyester, produced as under A

described 63.0 g

2 (benzoylmethylene) -l-ethyl-

naphtho- [1,2-d] thiazoline 2.5g

2,6-di-tert-butyl-p-cresol 2.5g

N-Methoxy-4-methylpyudinium p-toluene sulphonate ^ t

2 {N-Mcthy benzothiazoyhden) -methyldithioacctate ....... . 1.15 g

Fns- (N.N-dipropylaminophenyl) -

methane 1.25 g

Dichloroethane 2500.0 ml

The coating mixture began to set on standing to discolor.

To a 200-ml portion of the coating composition wurdenO, 02g2 _y-H droxy-3- _{P. P} end.no-5methyl-cyclopent-2-en-l-one added

In a corresponding manner, 0.02 g of 5,6-isopropylidene ascorbic acid were added to a further 200 ml portion of the coating compound added. In both cases there was further discoloration of the coating composition effectively prevented.

The three photosensitive coatings described were spin coated applied to an anodized aluminum support at 100 revolutions per minute. the dried plates were then for 2 weeks at 120 C and a relative humidity of 50% incubated.

The plate made from the coating composition without the reductone had a purple color Color cast. The plates made using the Beschicluangsmassen with a reductone did not show any discoloration and had a hue. the shade of the freshly prepared Plates corresponded.

B e 1 s ρ 1 e 1 3

Use of other leuco dyes in print-out coating compositions with a photosensitive binder.

The procedure described in Example 2 was repeated except that the tris- (N.N-dipropylaminophenyl) methane was replaced by THs (N.N-diäihylaminophenyl) methane or TrisiN.N-dimethylaminophenylinethane or BisiN.N-dieth \ laminophenyl) (N.N-diethylamino-o-mcth> lphen \ l) methane. Results corresponding to those described in Example 2 were obtained.

Claims (1)

Patent claims: 1. Coating compound for making light-sensitive Layers of aliscopying materials containing at least one leuco dye, a photo-oxidizing agent, contains a stabilizer and optionally an optionally photosensitive binder, characterized in that that there is a compound of the formula as a stabilizer