DE1622930A1 - Thermally activatable photographic recording material - Google Patents

Description

EASTMAN KODAK COMPANY, 343 * State Street, Rochester, New York, United States of America

Thermally activatable photographic recording material

The invention relates to a thermally activatable photographic material Recording material consisting of a carrier and at least one, at least one biazo compound and photosensitive ones containing at least one coupling component Layer"

It is known that diazo compounds, especially aromatic Diazonium salts, due to their sensitivity to light for the production of photographic recording materials let use. This is because exposure to light causes the diazo compounds to lose their ability to react with a coupling component to form a dye. It is believed,

009851/1770

that the diazo compounds react when exposed to light, with a replacement of the diazo group by a hydroxy * lated group takes place. In contrast, the diazo compounds are not destroyed in the unexposed areas, so that they in the alkaline development of an imagewise exposed photographic material with the coupling components present can react to form a dye, a positive reproduction of the original being obtained

The known photographic recording materials from Diazo types are developed either according to the known and customary wet (or semi-dry) processes or dry processes «

The wet method is applied to recording materials in its light-sensitive layer only one component, namely, a diazo compound _e optionally together with a stabilizer and other conventional additives, but does not contain coupling component. The exposed recording material is then developed with an alkaline solution containing a coupling component and a pH adjusting agent to form a dye in the unexposed areas. The developer solutions used have the disadvantage that they are generally corrosive and difficult to handle.

009852/1770

Recording materials are developed using the dry process, the one or more diazo compounds and one or more coupling coupons in their light-sensitive layer and preferably also contain other common additives, e.g. acidic stabilizers * The development is carried out by that the exposed recording material is exposed to an alkaline atmosphere, e.g. moist ammonia vapors, The dry process has numerous advantages over the wet process, but it suffers from them the disadvantage that the storage of ammonia and the handling of it are difficult. "

Also with the processes known from the USA patent 3 039 872, with the aromatic s-triazinyl as coupling components derivatives of the following general formula:

Cl

N N

IS S

C C - B

in the A © inen aminophenol © which indicates a polyphemol radical and "B has the same meaning as A © des- means a halogen atom, an amino or a hyiroxy radical where the triazine derivative is preferably used with a polymeric Yerlbimdüng

BATH ORIGINAL 0098S2 / 1770

Splitting off of the chlorine atom is condensed, must be used can be made alkaline for activation with alkaline vapors or an alkali-releasing agent.

The development process using caustic developer solutions or harmful ammonia steam are therefore more and has been displaced more by proceedings in which by

^ thermal activation alkali is released. The alkali-releasing agents can be incorporated into a layer of the recording material or used in the developing device. When heated, these agents decompose with the formation of alkaline substances and thus trigger the coupling reaction. For example, ammonium carbonate, bicarbonate, acetate and formate develop ammonia when heated. Due to the release of ammonia, urea and thiourea derivatives and organic amides are also suitable. When using the known, alkali-releasing agents

However , it is disadvantageous that they tend to crystallize out in the layer, which greatly impairs the shelf life of the storage materials they contain. In addition, numerous complicated measures are required in order that the release of the alkali can be controlled in the development apparatuses in a suitable manner.

The object of the invention is to provide a photographic recording material of the diazo type in which to trigger the

Bath 009 852/177 0

■ ' ■:': · ^{:. ::: Λ} ■■ ■■■. -./'■-: 1622930 ^:

Coupling reaction neither an alkaline atmosphere nor a ■ own alkali-releasing agent is required $ which » also very stable and can be activated by simple heating and whose photosensitive layer does not tend to crystallize out and is transparent, fog-free and not - is sticky, Λ.

The invention is based on the discovery that certain s-saturated Triazinylthioketone aldehydes and ketones, without applying to-% sätzlichen alkali or alkalifTeisetzender means with diazo compounds to dyes - are able to be coupled.

The present invention is a thermally aktivierbäres, photographic recording material comprising a support and at least a _t least one Diazoverbindüng and at least one coupling component containing light-sensitive layer, which is characterized in, '- that it contains as: coupling component is a substituted s-TTiazinylketon ".. -. or -thioketone of the general formula:

ζ I.

HN-NH H ₉ G CH

^ -: / - ■■■■ ■ ---- ■ - ,. -ßAD-önm ' XUQ

in which R- is a short-chain, optionally substituted alkyl, short-chain alkoxy, short-chain hydroxyalkyl or short-chain cycloalkyl radical and Z is a sulfur or oxygen atom

Advantageous short-chain alkyl radicals, which can optionally also be substituted, for example by a hydroxyl group, are such with ί to 8 carbon atoms, ζ.Β »methyl, ethyl, n-propyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, hydroxyethyl, or 1-hydroxyoctyl radicals.

Advantageous short-chain alkoxy radicals are those with 1 to 8 carbon atoms, s _e B _e methoxy, ethoxy, n-propoxy, n-butoxy or η-octoxy radicals.

Advantageous kuxzkettige cycloalkyl radicals are those with 4 to 8 carbon atoms, e.g. «cyclobutyl, cyclopentyl, cyclohexyl, Cycloheptyl or cyclooctyl radicals, the cyclohexyl radical being particularly is advantageous.

Advantageous 1-substituted s-triazine derivatives are e.g.

i-Methyi-tetrahydro-i-s-triazinthione,

i-n-propyl-tetrahydro-4-s-triazinthione, i-n-butyl-tetrahydro-4-s-triazinthione,

i-n-octyl-tetrahydro-4-s-triazinon,

1-Cyclohexyl-tetrahydro-4-s-triazijithioii,

00S85 2/177 0

1-Cyclohexyl-tetrahydro-4-a-triaiinon, i-Iiydroxyäthyl-tetraliydro-4-s-triazinthione, tn-irydroxyoctyl-tetrahydro-'A-S'-triazinthionjr in ^ HydroxyQCtyl-tetrÄhydrö-ii-triazinon tetrakydrQ-4 's-triazine thione in _{t-butoxy-tetraliydrb-4-s-tfIaiinon,} 1-octoxy-tetrahydro-4-s-tria2inon _l 1-n-pentoxy-tetrahydro * 4-s-tria2intliion.

The coupling components used in accordance with the invention are the use of alkali to initiate the coupling reaction Presumably superfluous because the saturated triazine derivative when heated in the way ünigelägertpder implemented is that the molecular structure formed acts like an alkali, without this rearrangement of the coupling ability of the friazinderiv & tes mit eiste © Diazoniumsalz.leidet «.

To produce the recording material according to the invention, the customary known diazo compounds can bsw. Diazonium salts are used «These known diazo compounds are light-sensitive and stable at room temperature and mechanical stirring. It is advantageous to use those diazonium salts that are soluble in water or other common solvents and that are soluble in the development of dark dyes to contrast well with the subsurface «-. "■":. "^; .. ^:; .: - /; ■ ■> ^:: . '..."' ■ - ■ -_ -.- ""'.

; ;;, h .. -original-

OQSf S2 / i

In a particularly advantageous manner, aromatic diazonium salts, their diazo grouping (-N = N) directly on a carbon atom of the aromatic nucleus is bound, is used. The positive valence of the diazo grouping is appropriate with one Anion saturated, e.g. with a halogen, phosphate, nitrate, Borate, oxalate or citrate anion. The diazonium salts can advantageously in the form of stabilized double salts can be used, for example, as metal halides or non-metal fluorides. For the formation of double salts, e.g. zinc chloride, Cadmium chloride, zinc chloride, boron trifluoride or fluoroboric acid be used. Typical suitable diazonium compounds are obtained e.g. by diazotization of the following amines:

p-amino-NfN-diinethyleneiline,

p-Amino-WjN-diethylaniline /

p-Arainö-N-ethylaniline _f

p-Amino ^ K-ethyl-N-ß-hydiroxyethylaniline, p-Amino-N-Hie thyl-N-ß * hydroxytthyl an i lin, p-Amino-NjN-di-ß-hydroxyäthylfiniliii,

^ m ·· toluidine '

809862/1770

- 9 - - ■■ - ■■ - ■ - ■■■■■■

3-aminocarbazole,

ρ-Amias-M ^ T ^ i äyi an 11 in,

p * Amino-N- (ß-hydroxyethyl) - aniline,.

p-amino-N- (2 _f 6-d ⁱ ibromb "enzyl) - aniliftj

p-AminO-N-benzyl-N-ethylaniline,

p-Amino-N, N-dimethyl-3-methy! aniline,

p-Araino-N-cyclohexyl-2-methoxyaniline,

p-Amino-N, N-di (ß-hydroxyethyl) -3-ätiioxyanilin,

p-Mino-3-garb oxy-ii ^ diethyl anil in,

p-Amino-2-hydroxynaphthalene-4-sulfonic acid, p-Amino-N-raorpholine ^ ZrS-dibutoxyaniline.

The recording material preferably also contains an acidic stabilizer to prevent premature coupling. The acidic stabilizers control the pH of the layer containing the diazonium salt and the coupling component, since some diazo dye may be formed even after prolonged storage at room temperature, although elevated temperatures are required to activate the coupling reaction. Advantageous acidic stabilizers are for example citric acid, acetic acid, tartaric acid, oxalic acid, boric acid, succinic acid, crotonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, 3-iiitrophthalsäure, Phesphorsäure, SuIfaminsäure and other Sulfaminsäurederivate, _ζ Φ Β. Cyclohexylsulfamic acid.

0098 5 2 / 177Ö

~ ^t0 ■■ - ■■ ^:

The recording materials of the invention can also contain other conventional additives, for example stabilizers and antifoggants or substances which prevent the discoloration of the developed images, e.g. thiourea, jhiocinnamine, naphthalene trisulfonic acid and the like reduce the amount of paper to be rolled up, eg ethylene glycol, glycerine or polyethylene w glycol; also additives to intensify the dye image, for example metal salts, for example zinc chloride, ammonium fat, nickel sulfate and the like; also coating aids, for example colloidal silicon dioxide and the like; also small amounts of wetting agents, for example saponin, lauryl sulfonate, cetylbenzenesulfonate, the oleic acid amide of N-methyltaurine and the like.

The photosensitive diazonium salt-containing layers of the recording material according to the invention can support or Contain binders that the coating composition prior to coating are mixed and after drying on the carrier form a film layer. Typical suitable binders are e.g. cellulose acetate, ethyl cellulose trimellitate, cellulose acetate phthalate, Ethyl cellulose hexahydrophthalate, cellulose ether phthalate, Cellulose acetate butyrate, cellulose butyrate, Cellulose butyrate hexahydrophthalate, ethyl cellulose, cellulose propionate and the like. The binder is usually in shape a solution in a volatile solvent, e.g. methanol,

009852/1770

622930

Acetone, Pichloromethane and other commonly known organic solvents, veniendet !, · ";,." ". ■

The calibration materials of the invention can contain a wide variety of known carriers. Depending on use * purpose, paper and foils made of plastic have proven to be advantageous, especially when the copy obtained should serve as a template again. In this case, transparent * films available from polymers are particularly suitable " net, * · Β * foils made from Polyfithyienterephthalatt Cellulosej. Cellulose triacetate, Cerllulö »fteCöt« tbutyr at. Cellules epr oplonät, Polycarbonates, polystyrenes, plysilphons and polyphenylenes oxides. Furthermore, H0I2, metals, e.g. steel, Copper, zinc and ^ aluminum * ceramic substances as well as glass and Textile materials as a carrier in Frag®.

To produce the according to the invention are the oiazoniuasalz, the coupling kGiapoaeiite and given £ ftlIs more seeds mixed with the beer, and is applied to a carrier in the usual way,

2.B »with the help of A1sstr # ifsa ^^ ■ ·

by hand. The material is then dried. In this way we would like -trocteße '5 <^ i ^ i; iwr' - ^: 7 | m ^ tl «ιι9p'aγβάt <» r endless mime * ^; <äig-free; ^ on & i ^ ei $ isititmtse ^

- 12 -

The photosensitive layer can have different thicknesses applied to the carrier. It has proven to be advantageous

2 instructed to coat the carrier material in such a way that per m Support area about 0.107 to 32.3 grams of dry photosensitive Material (0.01 to 3.0 g / sq »ft.) Is not required.

The recording material is used to generate an image or a copy of the invention imagewise exposed through an original which is located between a light source and the sensitized recording material. To exposure is For example, light energy of a wavelength range from about 3500 to 4500 R is suitable. After the exposure, this will be Recording material heated, with in the unexposed areas a dye image is formed, i.e. a positive copy of the original will be received.

Depending on the components used to produce the recording material, different development temperatures are suitable. Temperatures of about 93 to 204 ° C. have proven to be advantageous. The upper limit of the temperature range is mainly limited by the deformation and decomposition temperature of the carrier and the light-sensitive layer, with plastisch® carrier foils _f . E.g. cellulose acetate is particularly sensitive. ., lower temperatures. _

009852/1770

* -T 3.

The Aufzielehnungsmaterial the ^ invention is very läger resistant, toch after prolonged storage is practically not impaired "In experiments erfindungsgeniäßes of stability determination dignity recording material comprising cellulose acetate as carrier-rföl'ie for 3 days developed at 49® € and 35 relative humidity inkubieft _g exposed and * "It was found that the image obtained had the same good quality as the image of a non-incubated comparative material» ■ '■ "._'-;""..." -. ". _: ■; ; ^.: :: \ \ '' ■ '■ --- ■ _ -.-'_ ^{..;: ■:';} |.

The invention achieves that photographic recording materials are available * those for development. development of a latent image only need to be heated and which are characterized by a particularly good storability because the coupling components contained in them does not tend to crystallize out ", so that the light-sensitive Layer remained clear and transparent,

The following examples are intended to further illustrate the invention. Quantities are parts by weight, unless otherwise stated

Example 1 .- '"-■"""".." ^-:: \ ^r: ..';'' --- ^ ^";" ■ ":" ■■ - "" ---- ^": -..- '' ^-, - '""= ■■ -" ■ .-- V-' was 12 ieilen methyl alcohol and 5 parts of 6 Äceton prepared a solution of cellulose acetate TO parts ,; 25 ml of this. Solution were made with 0.5 g of p-diazodiätliylanilinziiikchlorid, 0.5 % Cyclohexyisulfäminsäüre and 0.5 ^ g 1-n-Pfopylwtetrlih) '' dro * 4-s- -. "Ν. ; V.,; -ν-; ::; .- v; . - '. .-; "^:; - :: ^v - . ':. ^: ; ■ / ■ ^; Bm OBiQlHM.

. . ■■■ "... ■ - 14 - ■■ '.

/ ■ -. ■■■■■■■■■. ^; ... '■.

triazinthion added. The mixture obtained was applied to a carrier film made of polyethylene terephthalate with a thickness of about O ₉ 076 mm, measured in the wet state or in such a state

Applied so tightly that about 16.2 g, calculated as dry weight (1.5 g / sq * ft _e ), were used per m of support surface. The dry film was then conditioned at about 20 ⁰ C dried was "transparent, clear (haze-free), hard (not sticky) and free from crystallization centers _e The dried recording material obtained was exposed imagewise through an original of a light source rich in ultraviolet light, exposed and passed through a conveyor belt development device -with a 10 second cycle over a heated TroEuael. The temperature of the drum was kept at 166 ° C. A positive copy of the original was obtained in the form of a brown dye image in the unexposed areas of good quality.

Example 2

The procedure of Example 1 was repeated except that the coupling component i-n-propyl-tetrahydro-4-s-triazinthione in the individual mixtures in each case by 0.5 g of the following Triazine derivatives was replaced:

1-methyl-tetrahydro-4 * s-triazinthione .;
in-Prop.yl-tetrahydro-4-s-triazinthione; i-ii-Butyl-tetrahydro-4-s ^ triazijithioni
n-octyl-tetrahydro-4-s-triazinon;

0 985 2/1770

- 15: -Λ. ■■ .- ■■:

i-cyclohexyl-tetralvydro-i-s-triazintliion;

in-IlydroxyoGtyl-totfahy-droM.-s-triazinonl 1-.5othoxy-tetrahydro-4 * s-triazinthioni in-Butoxytetrahydro-As-triazinonj
in-octoxy-tetrahydro-4-s-triazinon and 1-n-pentoxy * tetrahydro-4-s-triazinonone. ^

In all cases, positive brown dye images became the same good quality as described in Example 1.

Example 5

The procedure of Example 1 was repeated, except that a paper carrier was used instead of the polyester carrier film. A good quality positive dye image was obtained. ■■■ - '■': .-,

The Verfakrensweise of Beispieles- - !. was repeated _v 'except as ICuppiüngsk © mp © jiente ■ 1; used ^ nth Eutyl "tetra iydro" 4-s-tri®zinthion wwrd © »BAe-ertoiteß ©! the picture-bearing film was ^ again when. föriag ©: t pt. With ichtung.-e | e @ sV second _β as in example tZbefieferi ^ tsea ^ fergestellititnfci Äufäeiclmungsinmaterials used »· 0as« rhs3lt # Ä # _% . "i8, .eüe ^: -Dye image del pT4eh in all

Features practically completely those obtained in Example 1 Dye image.

009852 / 17.7 0

Claims (7)

P a te η t a η s P r ü c h e f I) JThermally activatable photographic recording material, consisting of a support and at least one photosensitive layer containing at least one diazo compound and at least one coupling component, characterized in that the coupling component is an s-triazinyl ketone or thioketone of the general For- | melts. ν It. HN NH ι ι HC. CH,
2 ν -. -Z. in R a short-chain, optionally substituted Alkyl, short-chain alkoxy or short-chain cycloalkyl radical and Z represents a sulfur or oxygen atom. 2) recording material according to claim 1, characterized in that, that there is an s-triazinylthioketone or as a coupling component s-triazinyl ketone of the given general formula contains » Q09852 / I7T0 /.■-■■ .: ■ .. ■ .- ■ '"-.- ■■ .. in which R is an alkyl radical having 1 to 8 carbon atoms Hydroxyalkyl radical having 1 to 8 carbon atoms or ein.Aikoxy radical having 1 to 8 carbon atoms. 3) recording material according to claim Z _9, characterized in that it contains a thioketone of the general formula given, in which R is an nP ^ ropylrest or a butyl radical. ^w 4) recording material according to claim 1, characterized in that it contains, as coupling component, an s-triazinylthioketone derivative of the general formula given, in which R is a cycloalkyl radical having 4 to 8 carbon atoms. 5) Recording material according to Claims 1 to 4, characterized in that it additionally contains an acid as a stabilizing agent. 6) recording material according to claims 1 and 5, characterized in that it is used as a coupling component i-methyl-tetrahydro-4-s-triazinthionej-1-n-propyl-tetrahydro-4-s-triazinthione; i-n-butyl-tetrahydro-4-s-triazinthione; i-n-octyl-tetrahydro-4-s-triazinon; . 009852/1770 i-cyclohexyl-tttrahydro-4-s-triazinthione; i-Cyclohexyl ^ tetrahydro-A-s-triazinoni i-Hydroxyethyl-tetrahydro-i-s-triazinthionj i-n-Hydroxyoctyl-tetrahydro-4-s-triazinthioni 1 • * n-Hydroxyoctyl-tetrahydro-4 «s-triazinon; i-methoxy-tetrahydro-4-s-triazinthione; 1-n-butoxy-tetrahydro-4-s * triazinoite; 1-n-octoxy-tetrahydro-4 * s-triÄzinon or 1-n-Pentöxy-tetrehydro «-4-s * triazinthione contains. ■■ · ■ - ■■■ ■ '■.'"■.■■■". ^:: . - ■ '. '~: " ^s · .-'"; - ■■ ■. ' * " - "" ■■■■■■■, '-' ■■■■ '- Ο: 7) recording material according to claims 1 to IX, characterized in that it contains an aromatic diazo compound, whose diazo group is bonded directly to a carbon atom of the aromatic nucleus ·; ■ '- ■; ■ BATH 2 / ^ 7 7ß ;; ' vr,