DE1572152A1 - Photographic suspension - Google Patents

Description

PATENT LAWYERS

DR.-ING. BY KREISLER DR.-ING. SCHÖNWALD 1572 152 DR.-ING. TH. MEYER DR. FUES

COLOGNE 1, DEICHMANNHAUS

Cologne, May 23, 1967 Mr / Wbs

Applicant:

EGG. du Pont de Nemours & Company

Wilmington, Delaware 19 898 United States of America

Photographic suspension

The invention relates to photographic compositions containing tanning developers Suspensions and a process for developing image-providing materials in the presence of such developers.

Tanning developers have been around in photographic for many years Emulsions and developers incorporated. Soluble tanning developer substances such as pyrocatechol and hydroquinone have various disadvantages, such as fogging during the Aging, loss of sensitivity during aging and diffusion through the gelatin, causing tanning of neighboring ones ITichtbild areas is caused. There are still limits to the use of some water-insoluble tanning agents. because they sublime during aging, producing unstable sensitometric properties, and because they harden the unexposed emulsion and affect its leaching.

The difficulties identified are caused by the photographic Suspensions of the invention eliminated. These photographic suspensions consist of light-sensitive silver halide grains in a water-permeable colloid. They are characterized by that they contain 0.01 to 0.3 moles of a polyhydroxy-spiro-bisindans included in the suspension. The alkylhydroxy-spiro-bisindan can be ortho- or para-substituted / hydroxyl groups in min-

Ö 0 9 8 1 7/1 5 7 5 - 2 -

desrens contain one of the aromatic rings. The Indane can also incorporated into the treatment solution or in the case of multi-layered light-sensitive materials can be accommodated in an auxiliary layer. These compounds have good developer properties for exposed or latent silver halide images and have an excellent tanning effect on the water-permeable ones Colloids, especially gelatin. .l.'after the procedure The invention develops exposed silver halide emulsions in the presence of the indane compound.

As a suspensoid, a colloidal system will hereinafter be referred to as k in multiple marriages! solid particles are present in dispersion, according to a preferred embodiment of the invention, a suspensoid is prepared by:;. neutralizing an alkaline solution containing up to> wt. $ 6 3,3,3 ', 3 ^l -i ¹ etrame "thyl-5, 6,5 ', e'-tetrahydroxy-spiro-bisindan (hereinafter referred to as "indan (I)"), gelatin in amounts of about 1 to 10% by weight and a water-miscible solvent for indan (I), for example 2- Methoxyethanol in amounts of up to 10% by weight The mixture obtained is then mixed with an uncured gelatin-silver halide emulsion in such a way that the actual concentration of indane (I) is in the range from about 0.01 mol to 0.5 mol The light-sensitive silver halide emulsion containing indan (I) is then preferably applied to a lacquered layer support in accordance with the information in Belgian patent 6 ^ 8 724 and German patent application P 41 121 IXa / 5? B After which with the help of aktiniscii After exposure to light, the light-sensitive material containing indane (I) is treated in an alkaline medium, usually a ρ / o aqueous potassium carbonate solution. Indan (I) develops the silver image and its oxidized form tans the gelatin in the image area, while in the non-image area, which is removed by washing with warm water, no erosion occurs. After washing with water, a hard-tanned silver-yellow-ink image remains as a relief on the marked support.

009817 / 157S

Indan (I) III: can be produced by condensation of Gr.tecnol with acetone according to the method described in Baker , J. Chem. See, page 167-J-1bo1, 19: 54-. Satisfactory results are also obtained using ^, 3? 5 ', p' - 'i'etraiaetiiyl-4,6,7,4', 6 ', ' / - ' -hexahydroxy-1,1' -spiro-bis -indan (hereinafter referred to as "Indan. II"). Indane (II) can be produced by condensation of polyhydric phenols with acetone in accordance with the information in Example 7 of the cited reference. Other alkylhydroxy-spiro-bis-indanes with hydroxyl groups substituted in the ortho or para position of the aromatic rings can be obtained in accordance with German patent 1,09,648. Such substances can be used in the same amounts as indane (I).

The tanning developer is usually added to the emulsion as a suspeneoid. The method of preparation of the suspensoids is not restricted to the embodiments described in the examples, since other methods of obtaining suspensoids from polyhydroxy-spiro-bis-indanes can also be used. In addition, such indanes can also be added directly to the emulsion. ^! dissolved substance can be added in a water-miscible organic solvent, or as a substance dissolved in the C ^ .- .. ase of a Üi-Waeser-Dispersicii. The tanning developers can be used in all customary hardened or uncured photographic emulsions. In ^ lei- ^ i-.ci * way kC ": uie: i these indane ii: developers or in iloinbiiiä-icn ir.with other developers soaped- wc-ru.en. Üie can be a.ior. In treatment ^ . ^ - iedien as IIisciu: criie ::: ul ^ icnen for iSyezeize the u: l _t: ekehrven übcrt-rn ^ ung breaking in:; the indanes, for example 1 and II can :: cu the Hilfssciiichren fetografischer _{Katerialieii;;.} You can learn: alone or in Kcrxi-na ^ ior- z.l'c other non-inheriting or tanning Enr - "- ick, in Erielcweise Alkyigallatt :; να; α Hydro chiiicn ar. .ve- ν a :: it "v / ground.

As Silterliaj.cj.eiiia-Eir.ulsionen kcr ^ -e :: the well-known fcjilterchlcriä. Silberbro: - ;. il u :: a oilberQcaic cder IIicczungen these silver salts contains: end :: R: .ulsicnen ir-frar; e. The 7erv; endux ~ der eifi :: - "- ir.:-:c-

ü L 9 8 1 7 / * S 7 S BATH ORIGINAL

According to the group of tanning developers, it is particularly useful in the case of emulsions of the wash-off type or in the case of precipitated and coagulating emulsions which are described in US Pat. No. 2 } 2-165 .

The preferred binder for the application of the tanning developers is gelatin. However, instead of gelatin, you can use other natural eggs, synthetic water-permeable organic colloidal Bi: i'le: .ii'crel, which are susceptible to crosslinked quinone tanning. Such substances include water permeable or w \ i c erlösliche polyvinyl alcohols and their derivatives, for example partially hydrolyzed polyvinyl acetates, polyvinyl ethers, and acetals ixe rroße a number outside the linking chain lying CiIOII -CH-groups. Furthermore, there are suitable: Hydrolyses Zwischenpolyinere of vinyl acetate and unsaturated addition pciyiierisierbare Verbindlangen such as maleic anhydride, acrylic acid "■ χϊΛ Herhacrylsänreäthylester as styrene Suitable colloids of the zule-; 2o-mentioned type are US Patent 2 276 5> 22, ._ Jf6 325th and d. 547. The polyvinyl-α c -: - c als that can be used include pcycyl-ylacealdehyde acetal, polyvinyl butyraldehyde acetal, and polyvinyl chloride-o-sulfobenzaldehyde acetal Poly-N-vinyllactams c-: in accordance with the information in US Pat. No. 2,495,918, the .-. Ydropj-ilen Kischpolneren of IT-Acrylamidoalkylbetaide according to 'the "oA-Patentschrift-G 2 iiJ3 650 and hydrophilic cellulose ethers and cellulose surfactants.

In addition to the preferred padded layer supports, all suitable transparent plastic layer supports for emulsion layers are possible. Examples: The cellulose-based layer supports such as cellulose ac e ~ z ar, cellulose triacetate or cellulose mixed esters. Polymerized vinyl compounds, such as a non-polymerized vinyl acetate / vinyl chloride, and polysyrene and polymerized acrylates, were also incorporated with the invention. Furthermore, the following rrätferi'clien BEV / äxirt ;: The from the polyesterification of a dicarboxylic;: ^i: v.re uiii a zv / eivverrigen alcohol according to the US Patent

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157/152

font 2,779,684 and the patents listed here Films, the polyethylene terephthalate-isophthalate products of British Patent 766 290 and Canadian Patent 562 672 and the condensation products of terephthalic acid and dimethyl terephthalic acid with propylene glycol, diethylene glycol, Tetramethylene glycol or cyclohexane-1,4-dimethanol (hexahydro-p-xylene alcohol) and the films of U.S. Patent 3,052,543. The polyester films are great because of their dimensional stability particularly suitable.

In addition to the auxiliaries used in the production of a suspensoid of indane (I) such as water-miscible solvents, e.g. methoxyethanol, various other auxiliaries can be used be incorporated into the emulsion. These include surfactants Substances such as sodium dodecyl sulfate, auxiliary developers and other tanning agents such as propyl gallate, alkyl gallates and hydroquinone. The emulsion can contain dyes such as tartrazine (Color index »0.1. 640) tinting dyes such as phenyl biguanide mercaptobenzothiazole and similar substances as disclosed in U.S. Patent 2,668,113; aside from that hardeners such as chrome alum, formaldehyde; Matting E. means j optical brightening means j image color modifying agent; Use sensitizers and optical sensitizers.

The use of tanning developers such as Indan (I) is particularly beneficial in the production of reproductions of drawings, Maps, line copies and halftone copies, which can easily be reproduced by drawing on the matt surface and / or damp Erasing the relief image can be revised. The use of a substance such as indane (I) with hydroxyl groups in ortho- or ■ para position on the aromatic rings is particularly appropriate in conjunction with any binder that is quinone tanning is accessible.

Indan (I) has particular advantages over the use of other tanning developers. Because it is not fleeting. This is

S

C09817M57S * ^AD

important to use the tanning agent during the production of the photographic {Substance is added as there is none during aging volatilization-related produkbinstabixicäi has the same effect these other genetics like! catechol and tertiary suuyikauecho ^ to do.

In addition, it is a question of indan (Ij and- i; ai_ Ox / da ^ iorißprodui- :ten non-migrating excesses. Dadurc; - 1; jü the effect during development is limited to the image area, while a migration This property is done;; to the adjacent llichtbiidbereichen nicr.. provides eir.e from ^ ^ e ezeiciine Acvrasc;, .- length image sharpness safe.

In the same way, the silver image can be removed by bleaching in a known manner and the materials containing indane (I) can be used for known coloring processes; will.

Another advantage is that the oxidized i'Orm des Indans (I) is an excellent tanning agent and quick delivers very hard images. This is necessary for wash-out products or in the formation of relief images for photomechanical ones Copying process.

The next few examples illustrate the invention. All 'Quantities are to be regarded as weight information.

• - 7 -009817 / 157S

iiei :: play Ί

An un,:; eiiäruete Gelai ine-oilberchlorid-Eiiulsion, the 1, i> Hole üi j berchlorid and ^ L * . GeIarine contained, was coagulate ^ ^ ev.'Hiic-.CJi iuid in Ge: -enw? Iri vcr 1._; '' r gelatine redispeiviert (ver.cl. UbA-i'irentoc ':.''IJ! . ,. WV: "1 ^ i.) · The emulsion was connected to;,» folj: eiiue ΰιοΓ.Ό su _; oTüfL .:

1.) Ί ι; eini · ΊΟ ^ i; en waijsi-i / en] ju;. 'vuir ue :: Ih, iriiu.calzes from L'-Coco-BA :: iJnoT>ropiona;;alc;"Ooco" ln \ a iascnuii ^ the Koh3eiiv: a. ^% .: ^- cr.-tt i'rradik'iie of high molecular weight to be regarded as those enrc]> rest in .ien Ecterii von Kokocniüsbl vc.'lit -on eiiu'c ^ .ieiilich in dei * HeiheniOlpe abi ' allen- <: er Lon.:·:: Λ '^ w ion, the Xi'iur.vi-, Ilyristyl-, Pal ::: it; yl-, üaprvl; ^] C; i;' ryl- and i ... e; -l-Re ^ ie,

ti.) _ :, C tJ a Ii> iii (; en v.-ä.wriren Tartra ^ inlc-Jiui-; · (0.1.-64C, where CI.; ieh on l ^ .M. Rome's Color-Inlex . Ί. Edition, Society el " Dye. · A;: i Gc.i. Urin :: .., Ί924-, beziei ;-), J.) Vb L einor ■> j: οι. Vräij .. 'igen l. ^ 'riuK.acdecyisuifatlösunfj, ^ι ί-) V? g a ■.> ji. er. wäriren Hr'aii'cxylai ^ iiii ^ drcchlcridlösun ^, {, ·.) .aid a; ^^ ciiu: _H : , ent :: ali-e: .ii; u _; _ 3 ,; ·.; ■ ',>' -xetra:.: et; i: "i-

1 Λ *

2SO c:;. ' Ai. _t ylalkoii.ol u: k. 60 ^ · c: r'water.

Ailen the ajit *; & e. .Uit:.. Ic :: wui'de av; .. 'a :: i: ^ ne of detention: C: .ic: ru from jrep ^ ^ atre eii,:: \ . ".-. erien Pclyeetei '-. jjiiicr.rvrä ;; er enti: r.rec: .enc. the Belgian P; re ::; iO Γίίΐ or- 724: \ ui \ je2or.-en. The order eri'ol -_ ": e in a Ken. -o vci. C :: ig Aj "Cl / d ~ ^t ~. The auitreso _e ene Er.ul.::ici. Vrurie then yetrecknev.

Dat: borrowed-e: .. v: 'i ::. Ilic-.e Ilaxerial ^ eifve :: ami die rolgenäne ^ entirc- : aetric <? r. : r.i T'hysi "alischen Ei, enschaiven:

bc.i: -l _:::: u ^: - there? Eir-p ^ ind- Ί Kin. J Hin. au_ ^ e-cdicl-. e-

licl'-lceit D :: "x Entv, -. Enrv.-. ve :: Er-Ulsicr. in

Ws.? s he

v_,

.0 09 817 / $ 157

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After exposure to a negative using a carbon arc light source (1 minute) the material was developed in a 5% aqueous potassium carbonate developer solution at 20 for 1 minute. The non-image areas could be easily washed out with warm water. After the water treatment there remained a hard; it, tanned relief image on the matt surface of the substrate.

Example 2

Example 1 was repeated with the exception that the exposed photosensitive material was 5 minutes at 21 ° before development : r.i "; water washed and then, as described in example 1 :;. eii, was developed. This working method proved that the Indan® he did not tend to migrate to neighboring oaks, as did yours finally tanned clear relief image emerged.

Example 3

Unhardened, not very sensitive gelatin silver chloride emulsion was corresponding to a coating of 25 mg AgCl / dm a matted acrylic acid layer underlaid with an adhesive layer applied according to the information in the Belgian patent specification 6p8 724 had been made. The emulsion was accordingly Example 1 exposed with a negative.

A developer solution A was prepared as follows:

Solution a

Sodium carbonate (anhydrous) 10 g

tetraaydroxy-spiro-bis-indan 1 g Hest: water at 1000 cnr

The exposed photosensitive material was developed in solution A at ko ° for one minute. The exposed areas were

GU9817 / 1575 ~ ⁹ "

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developed and tanned while the unexposed areas are none Tanning or developer exposure showed. The latter were in warm Washed off with water, after which a gelatin-silver image remained as a relief on the matted surface of the support.

To further illustrate the tanning effect of indane (I) the same emulsion as in example 3 was exposed and developed as described in the first half of this example, with the exception that the developer did not contain any indane (I). There was no image development in the carbonate developer showing the utility of indane (I) as a tanning agent and as a developer, the exposed silver halide reduced to silver.

Example 4-

The following suspensoid was made:

Suspensoid A

3.3% aqueous gelatin 150 g

3 η NaOH 2.5 cm ⁵

10% aqueous NapSO ^ solution 1.0 g

Solution of 3 _? 3,3 '? 3'-tetramethyl-5,6,5' ₅ 6'-tetrahydroxy-spiro-bis-

indane in 2-methoxyethanol / 1 g indane (I) in 6 cur 2-methoxyethanol /

6.0 cm

The components of Suspensoid A were formed with each other mixed in a haze-like solution. To get a clear greenish blue mixture with a pH of 11.5, 1 cur of a 3N NaOH was added to the mixture and then slowly with 6.5 cnr of a 1.5 η HpSO ^ solution under adjustment a pH of 6.5 and precipitation of indane (I) neutralized .

! The following ingredients were added to the precipitated Suspensoid A. :

"A _D OR, Ü, NAL 3θ» · 17 / 1β7Ι

-ίο- 157; j 52

d.0 #Lge aqueous gelatin 150 r

washed AgCl emulsion (Hole AgCl) 0.15 Hole 2 / & Lge ilethanol pung of phenylbiguanicimercaptobenzothia'zol

10 ^liter ethereal solution of propyl gallate aqueous iartrazine (CI. 640) sodium lauryl sulfa :
aqueous hydroxylamine sulfate N-coco-B-amino-propionate (same mixture as in example 1)

20th C. 20th 25th K 7, 5 ü 3,

The emulsion obtained nit a pH value of y o was AAnn according to Example 1 to a marked: en oCiiicntträger mounted. The applied emulsion; tired then aged, exposed and according to Example 1 at v / icke 1 "C. The censitonebriscueri and physical properties were the following:

Relative
Sensation
opportunity D. Max Veil 3 Hin.
Dev. Melting point 100
90 3,
2, 12th
73 1 Hin.
Errcw. 0.25
0.15 32 °
32 ° Irish
Accelerated
Aging (as in
Example 1) 0.07
0.06

The unexposed areas showed good washout properties. They left a tanned, hard relief image on the matted one Carrier.

Example 5

The following suspensoid was made:

Suspensoid B

Component A

7.2% aqueous gelatin 10% aqueous Na ^ SO ^ solution 2 η NaOH

GG9817 / 1S7S

1725 S. 3 - 11 - 17th G 8AD ORtGlNAt 25th cm

157-52

Component d

2-ethoxyethylene: iol 1c6 cm ^y

Methanol 194 cm ⁵

Phenylbioisaidmercaptobensothiazole 4 g

Propyl gallate 20 g

3,5,3 ', 3'-ietramethyl-H, 6,5 ·, 6'-teti ^ ahydroxy-cpiro-biß-iiidan 10 g

Component d was merged with component 1 and aie received i; e Miijcniuif lan.:ssuii within?. Minutes with 115 cm ¹ '0.5 η H ^ SO ₂ , ixeatraliiiiert;

De ::. Sut] .: ei ..; ^ Id 1: vrardei Γοΐ-those components added:

i-cner.e A _t ; '0L.Er.ulf5ion Λ ^; "Mol

-iji ^ ei * wä.i-ri: es Tartrauin (CI.

».: 'I6i _r ; eiJ v. ^r: L, ^r : crl-: es Natriundoiec.vl-

Kuifa: '75 G

c ieises wri: '.; ri es liydrox ^^ laainauirat 7; b

'~ \' , 'oi.jec v; ^: -;: ri -es Ii-Ccc.c-3-A: ninoprc- ■. '■ ion; ·: ^ .ic .-: .- * iche;: i ^ churir as in

Which he:;·----. <::: e ':. chter.pf indlic ^ e} i: "jisic :: was danix v; ie in: Beispie "i auf eir.e: i r.ar fourth en iJCi.ichr-: rä ~ er aui'gebr & ciit. The raised üruisicr. vnirde olds and en: £ ■. based on example 1 partially travel

How folrV v.-urdc a developer made:

Developer G

Distilled water 9 ^ 9 above sea level

KpOO, (anhydrous) 3 ^, 2 g

NaOH 3.1 g

K ^ SO, (anhydrous) 4.9 g

KBr ■ C, 21 g

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The exposed photosensitive material was in developer 0 developed while training a finished in less than 15 seconds Image. The unexposed areas were easily washed out with water at 32 ° after soaking in the developer for 15 seconds. With regard to the wash-out properties, no change could be observed after treatment in developer C for 20 minutes will. The sensitometric properties after 1 minute development in developer C were the following:

Eelative sensation

veil

1 min. 3 min. Liability D max Dev. Dev. Melting point

.Fresh

Accelerated aging (as in example 1)

100

90

2.22 0.02

0.03

37

1.81 0.01 0.02

After washing out, a tanned relief image remained on the Support.

Example 6

Example 5 was repeated with the exception that 1/3 of the gelatin in the photographic emulsion was replaced by a gelatin polymer component which had been obtained by copolymerizing 8 parts of vinylidene chloride and 8 parts of ethyl acrylate in the presence of 1/4 parts of gelatin (cf. Example Λ of Belgian patent specification 658 724). Before the emulsion was applied to a matted layer support according to Example 1, 400 g of a 5% aqueous hydroquinone solution were added to the emulsion. Aging, exposure, development and assessment corresponded to: Example 1. The emulsion containing the tanning agent indan (I) showed the following sensitometric properties:

Fresh

Accelerated aging (as in example 1)

Relative sensitivity

100

veil

D max

1 min.
Dev.

3 min. Dev.

0 Q #i 1 7 /

0.02 0.19

° ^'04

Melting point 36 °

572152

The incorporation of hydroquinone into the emulsion led to an increased D max, but at the same time to an increase in the melting point. The image hardness and the washout properties were superior to those obtained when using hydroquinone without any addition of indane (I). Similar results were obtained when the gelatin of Example 5 was replaced with 100 % of the gelatin polymer ingredient.

Example 7

Example 1 was repeated except that all ingredients were reduced to 1/10 of the scale and ingredient (5) was a mixture of indane (II), 32 cm dimethylformamide, 25 cm ethanol and 48 cm water. Indan (II) was according to the information from ffisher , Furlong and Grant in J. Am. Ohem. Soc, 58, pp. 820-22 (1936), Example 6.

The emulsion coating was applied in an amount of 45 mg AgCl / dm and showed the following sensitometric and physical properties:

Krisch

7 days at 49 and 65 % relative
Moisture aged

Relative sensitivity

100

96

D max

veil

1 min.
Dev.

3.25 0.04

0.07

2.84 0.04 0.10

Melting point

ό Min. of the broken-up dev. ten emulsion ia water

35 *

39 ^l

After exposure to a negative using a carbon arc light source (1 minute) the photosensitive material was immersed in a 5% aqueous potassium carbonate developing solution at 20 for 1 minute developed. The photo areas were then lightly washed out with v / lean water leaving a hard tan Relief image on the matted support surface.

C 19

1 7/1 5 7 5

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Claims (3)

Patents 1) Photographic ouspension, beiicehend from licliöer.i i'inaliciien "jilberiialogrenidkörnern wassei'aurchiässigen in a colloid, characterized in that a Po Ij hydroxy-spiro-bis-indane present in the suspension from 0.01 to 0.5 Hole. d.) Suspension according to claim 1, characterized in that gelatin or a mixture of gelatin with a yinylidene chloride / alkyl acrylate high polymer was present as colloid ¹ ; 3.) Suspension according to claim 1 and 2, characterized in that the indane 3,3,3 ', 3' -Te-cramethTl-5,6,5 ¹ , ö'-teTrahydroxy-cpiro-bisindan or 3,3, 3 ', 3' -Tetra-4-, 6,7,4 ¹ , 6 ·, 7'-Hexahydro- '], 1' -spirobis-indane. U -.)) JOtographic process uncer use of photographic Suspension according to claims 1 to 5 with development of an exposed one Silver halogen emulsion, characterized in that developing takes place in the presence of a polyhydroxy-spiro-bis-indane; 5 ·) Method according to claim 4, characterized gekennzeichneτ that dass_das Indan is present in an aqueous alkaline developer solution. BATH