DE2254358A1 - THE USE OF COMPOUNDS RELEASING MERCAPTANE IN SILVER HALOGENIDE EMULSIONS OF THE LIPPMANN TYPE - Google Patents

Description

• AGFA-G EVAERT AKTIENGESELLSCHAFT LEVERKUSEN ·

The use of mercaptan-releasing compounds in Lippmann-type silver halide emulsions. ·

Priority: Great Britain, November 10th W. "Note No. 52 290/71 '■ ·

• The present invention relates to the use in silver halide photography of compounds which are aliphatic ^, aromatic or heterocyclic mer-. release captane, and the use of these compounds in silver halide emulsions, especially silver halide emulsions of the Lippmann type.

Lippmarin emulsions, which are usually an average Having grain sizes of less than 100 mn are special Significance for the production of photographic plates or films with high resolution, for use in microphotography, for recording nuclear physical phenomena, for the production of masks in the production of microelectronic vision, integrated circuits, for use in holography, for high-quality data storage, etc.

In the production of microelectronic integrated circuits, for example, drawings are made on a greatly enlarged scale of the various successive masks that are necessary to produce an integrated circuit. provide, after which the drawings will be reduced if necessary be reproduced in successive steps, and on a photo- • fjraphischen IJppmaravPlatfce or ent ^ rechadem Fümnaterial, to thereby form the ready-mask. Through various photographic and chemical steps (photo-etching of lacquered plates), the images of the masks produced in this way are transferred to the surface on which the integrated circuit is to be produced in order to achieve the required switching

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to manufacture circular elements.

The photographic materials for use in manufacture of masks as described above should have high resolution and sharpness and a allow correct reproduction of image dimensions. One hits with Lippmann materials with a high resolution however, to special problems both in the inverse process and in the negative process. The generated images show e.g. often in certain areas distortions of image details due to the mutual influence of closely spaced Image details, and image sharpness does not always meet the requirements.

It has now been found that the above-mentioned adverse effects reduced odor can be avoided by incorporating catechol derivatives into the Lippmann erasions, which correspond to the following general formula:

OR
I.

-OR

in which:

H hydrogen, acyl e.g. acetyl, haloacyl e.g. haloacetyl or Aoyl, which bears a cjiaternary ammonium group,

H ^ hydrogen, a halogen atom, an alkyl, aryl or alkoxy group, and

Ko an aliphatic group, in particular alkyl, substituted alkyl, for example alkyl which is substituted with carboxy, with aryl or with a heterocycle, an aromatic group, in particular aryl, substituted aryl, for example aryl »that with halogen or with C ₁ -C ₁ - alkyl is substituted or, preferably, a heterocyclic group, for example a 1-gubstituicrte 5-tetrazolyl or 3-triazolyl or ^e i ^ e-2 Benzfchiazolyl- group '. :

Representative examples of compounds similar to the above

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general formula and suitable for use The following are suitable for the present invention:

1. J-methoxy-e-phenylthio-catechol (calc. % ± (1961) 1267-76)

2. 4- (1-Phenyl-5-tetrazolylthio) -5-t-butyl "pyrocatechol (J.Org .. Chem. 2 £ (1964) 539).

5. 4- (1-Phenyl ~ 5-tetrazolylthio) -5-phenylpyrocatechol (J.Org. Chem. 29 (1964) 589). "·

4. J-Benzylthio ^ jG-di-t-butylpyrocatechol (German patent

■ font 1 140 944)
5 x 4- (1-phenyl-5-tetrazolylthio) catechol

6. x- (2-Benzthiazolylthio) -pyrocatechol

7. x- (1-Phenyl-3-triazolylthio) -pyrocatechol

8. 1 ~ Phenyl-5- (3, ^z t-diacetoxyphenyl) tetrazole

The structure of Yertindungen 6 and 7 is only incompletely determined as far as the position of the heterocyclic thio group is concerned; this is indicated by the use of χ in place of a number in the structure, although in this case the position is likely to be the 4-position.

The compounds of the above general formula in which R is not H are the chemically latent forms of those compounds in which E = H and can be prepared by methods described in the literature, for example in US Pat. No. 3,246,988 and US Pat Belgian patent 734 140 .

The Brenzcatecliinderivate, which besides the thio group have a group R ^ different from H, e.g. alkyl, aryl, alkoxy etc., can be prepared, as it is shown in J.Org.Chem. · 2 ° ^ (1964), 589 , by allowing the correspondingly substituted o-benzoquinones to react with the corresponding aliphatic, aromatic or heterocyclic thiol. Since the unsub-substituted o-benzocliinone (IL = H) is unstable, this ver-Jäaren is less satisfactory for the preparation of the hitherto unknown catechol derivatives in which R = H. It has been found that the new catechol derivatives, wherein R ^ = H and Ii _{0 is} a heterocycle, can be satisfactorily prepared by

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Reaction of the heterocyclic mercapto compounds rait ochinon the in situ from catechol and an oxidizing agent, e.g. potassium hexacyanoferrate (III) is formed.

The synthesis of the Connections 5 through 8 illustrated.

Establishment 1 : connection ^

To a solution of 13 g (0.118 mole) catechol, 17.8 g (0.1 mole) i-phenyl-5-mercaptotetrazole and 50 g sodium acetate trihydrate in 180 ml of water, a solution of 65 g (0.2 mol) of potassium hexacyanoferrate (III) and 50 g of sodium acetate trihydrate in 150 ml of water were added at room temperature with stirring. the The mixture is stirred for one hour, whereupon the precipitate is suction filtered and recrystallized from 200 ml of methanol. Yield: 20 g (70%). Melting point: 164 °.

Preparation 2 : Compound 6 ** 'A solution is made to a mixture of 13 g (0.118 mol) of pyrocatechol and 16.7 g (0.1 mol) of 2-mercaptobenzothiazole in 150 ml of acetone and 50 g of sodium acetate trihydrate in 50 ml of water 65. E (0.2 mol) of potassium hexacyanoferrate (III) and 50 g of sodium acetate trihydrate in 150 ml of water at 15 ° with stirring. The mixture is stirred for 30 minutes, after which the precipitated salts are filtered off and the filtrate is poured into water. The precipitate is purified by continuous extraction with methylene chloride / methanol (10: 1).
Yield: 14 g <5 %). Melting point: 1%.

Manufacture 3 : Verbir.Juse 7

A solution of 0.114 mol of o-benzoquinone (Eer. £ 7, 4745) in 750 ml of anhydrous Eth ^ r toi 10 ° are added dropwise with stirring. The quinone solution becomes discolored and the precipitate dissolves almost completely. After one hour the solution is filtered and concentrated by evaporation. The residue is recrystallized from a minimal amount of methanol.
Yield: 11.5 K ( ^{/ (} 0 %). Melting point: 198 °.

BATH ORIGINAL 309820/1056

Production 4 : connection B

To a solution of 28.6 g (0.1 mol) of compound 5 in 120 ml of dioxane, which contains 2.4 g (0.1 mol) of magnesium turnings, 39 g (o; 5 mol) of acetyl chloride were added dropwise. The mixture is refluxed for 24 hours and then filtered. The filtrate is evaporated and the residue extracted with 100 ml of benzene. The insoluble residue is isolated and the benzene solution is filtered and evaporated. ,. . - · ■ yield; 34 g (92%). Melting point: <50 ° G.

Both in reverse processing and negative processing of Lippmann emulsions a? there. the use of the compounds, which correspond to the above formula, an increase in image sharpness, especially the sharpness in fine details and a beneficial effect on image detail distortion. It was also found that * those used according to the invention Connections one in the reverse processing of Lippmann materials occasionally observed and probably due to residual developer oxidation products Counteracts yellowing. . ·

The present invention compounds to be used are the <· emulsion layer by adding, either as a solution or dispersion incorporated to the Giesszusamraensetzungen the Lippmann emulsion.

The concentration of the compounds according to the invention _used:; depends on the characteristic properties of both the ge ^; wanted connection as well as the emulsion and is therefore best determined by trial. In most cases the optimum concentration for the silver halide emulsion is: between about 20 mg and about 2 g, preferably between about; 100 mg and 1 g per mole of silver halide,

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- & -

The thickness of the emulsion layer of a photographic material in accordance with the present invention is generally between about 3 microns and about 8 microns; the average grain size the silver halide grains are generally a few * than 80 run. The ratio of the silver halide to the hydrophilic, colloidal binder in the Lippmann emulsion according to the present invention Invention is preferably at least 1: 2 and at most 4: 1.

The ßLLLberhalogenid Lippmann emulsions can according to process which are well known - and described in the literature (see e.g. P.Glafkides "Photographic Chemistry", Volume 1, 1958, Geiten 365-368, Mees / James "The Theory of the Photographic Process ", 1966, p. J56 and National Physical Laboratory "Notes on Applied Science", No. 20: "Small Scale preparation of fine-grain (colloidal) Photographic Emulsions", BRA. Crawford, London, 1960). You also know according to one Process described in Belgian patent 765 029.

Very fine-grain silver halide Lippmann emulsions can be obtained by carrying out the precipitation of the silver halide in the presence of heterocyclic mercapto compounds, as described in British Patent 1,204,623, or in the presence of compounds as described in US Pat Belgian patents 758 103 and 758 242 became.

The hydrophilic used as a support for the silver halide Colloid can be any of the general hydrophilic colloids used in photographic light-sensitive emulsions can be used, e.g. gelatine, albuaini zein, casein, alginic acid, a cellulose derivative such as carboxymethyl cellulose, a synthetic, hydrophilic colloid such as polyvinyl alcohol and Poly-N-vinylpyrrolidone, etc. If desired; » can be contractual Mixtures of two or more colloids can be used to disperse the silver halide

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Various silver salts can be used as a photosensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide, silver bromide and silver chlorobroirgodide. Silver bromide emulsions with. an iodide content of at most 8 Mo 1-% "and an average grain size of at most 80 nm are preferred.

The emulsions can be applied to many photographic emulsion supports be applied. Typical carriers are cellulose ester film, Polyvinyl acetal film, polystyrene film, polyethylene terephthalate film and related films of resinous material such as paper and glass. In the manufacture of panel materials of high Resolution for the manufacture of masks for use in the electronics industry will most advantageously be glass substrates used because of their high dimensional stability.

The light-sensitive emulsions in question can be both chemically and be visually sensitized.

You can use any of the well-known, spectral sensitivities, such as cyanines and merocyanine dyes, for photographic, silver halide photosensitive materials spectrally sensitized will. The silver halide solutions according to the invention for the production of microelectronic masks are most advantageously sensitized to the green region of the spectrum. The light for exposure is preferably in part the wavelength for which the emulsion is spectrally sensitized has been.

The chemical sensitization of the emulsions happens on any way, e.g. by maturing with naturally active gelatin or with small amounts of sulfur-containing compounds, e.g. Allyl thiocyanate, allyl thiourea, sodium thiosulfate, etc. The emulsions can also be sensitized with reducing agents, such as according to that in the French patent specification 1 146 955 and Belgian patent 568 687 Process with iminoaminomethanesulfinic acid compounds as described in British Patent 789,823

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or with small amounts of certain precious metal compounds, such as gold, piatina, palladium, iridium, ruthenium and rhodium compounds take place.

The emulsions can further contain compounds which sensitize the emulsion by accelerating development, e.g. Alkylene oxide polymers such as the alkylene oxide condensation products as described, inter alia, in the American patents

2,551,832 and 2,533,990, and in British Patent Specifications 920 637, 940 051 945 340 991 608 and in Patent der'belgischen 64-8 710. Other development accelerating compounds are known onium compounds such as quaternary ammonium, Quaterna 're phosphonium and ternary sulfonium compounds as well as onium derivatives of amino-N-oxides as described in British patent specification 1 121 696.

The emulsions can also be stabilizers, e.g. heterocyclic nitrogen-containing thioxo compounds such as benzothiazoline-2-thione and 1-phenyl-2-tetrazoline-5-thione and compounds of the hydroxytriazolopyrimidine type. You can also use Mercury compounds such as those described in Belgian patents 524 121 and 677 357, British Patent specification 1,173,609 and the American patent specification

3 179 520 are stabilized.

The emulsions can also contain light-absorbing dyes that are chosen to absorb light of the wavelength at which the material is exposed, so that Scattering and reflection of light within the photographic Material is reduced. You can find more information about these dyes one in Belgian patents 699 375 and 742 954. The Dyes are preferably used in amounts such that, per micron thickness of the emulsion layer, a density between 0.05 and 0.20, similarly in the spectral range of exposure dark light, receives.

In the emulsions according to the present invention, Jedor Hardeners can be used for hydrophilic colloids, such as chromium,

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: 254358

Aluminum and zirconium salts, formaldehyde, bialdehyde, K7 / droxyaldehyde. Acrolein, glyoxal, halogen-substituted aldehyde acids such as mucochloric acid and mucobromic acid, diketones such as divinyl ketone, compounds which carry one or more viaisulphonyl groups such as divinylsulphone, ^, J, 5- ^ rivinylsulphonyl benzene, hexahydro-carbonyliazines. ,, Halogenacetyl and / or acyl groups. carry like 1,3 ₅ 5-2riacryloylhexahydro-1 ₉ 3 »5-triasin, 1,5- ~ 3) iacryloyl-5-acetylhexahydro- _{1 -, 3i5-triazine 5} 1 ^, ijMirichloraccbyl- · hexahydro-1,3 , 5-triazine, etc. - - ·

To the adhesion of the emulsion. die'glass support during manufacture of algae material with a high resolution can reinforce the Siliarumveröindmigenj those in the Belgian Patent specification 741.820, are incorporated into the emulsion »

The light-sensitive egg sions can also contain all other areas of ingredients, such as lfieicJbmachej? _g GiesszusätaG ^ ugv.o

Although the Yerbinänngen ₉ those of the o'beag ^ assinte'üj general

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Formula correspond to _s liesonaess zur- fem- ^ siacitMg ia! »Ippmatm · = 'emulsions described Hordes, sigia, _G !: Oss © s sie & r & u ia feBdei-ou light sensitivelisa Silber2i & l © g @ nia © a'ulsi © seB ire ^ ^ saaefc i "; ord5n ₇ , UR increased sharpness su cause"? 3i® lfeseindimgsa ά © 3? Inventlip.s are Silberhalogsnident ^ icklespsubstssiseri "oad s & tssjH sr.twic" kli2: ug- ^r preventive fi MerGa-otES. ¹ ? ΐϊ? © ίο lirfi & s- I ^ Pimta'si <? sQv? oli.l is

i ?; ^: i _; TL ClIfi, fc ^ iO / i. Ιλϊ ^ S'äfe.oaiSrOSiSi. ^ ISCfcefö

'Lx. ιοί:, - Ss- ¹ Se ^.

sssy ',;} ^ s, v el ο ;. "

! (Rl i ^; i ^cc ", V (■ '■ / < ■'.": I'U C ^ S

mm s

According to the invention, the development retarder is released in an image-wise manner in the emulsion, which results in a changed graininess. The brenzcatecaine developer locally, restores the aromatic, primary amino acid developer substance from '' s e ine η Ox i ei ati ο 1 1 ξ ρ γ ο ά iik t en.

The following examples illustrate the present invention. ■ '"

I) in * chg 1 e ι ch ζ e 11 ige η to a at ζ a S i l'b e rn itra 11 solution im d a r K al i umb r ο in id 1 ö c un β ζ u ' a 3 % aqueous η G e 1 ati η e 1 ö acid is a silver brocid emulsion with 72 g of silver bromide and. 93 S Ge 1 at ine per Ki 1 ogr aiam he rge ste 111 * The Päl ment 3 "conditional-ungeri are set so that a Lippjaann enailsion with e in ermi, 11 1 er e η Ko r ng: r ο ss; ^: ; ν c n. 70 mn received en vi r & ·.

wrong

nf r ι ι f r

-u in fi "τη ·" m * ι ICO (s L Llo

^f lc (naif ^ u, FITL H ¹ bE ^"i Ji ^l Tf hr η" ■ 11 ι ^J Γ ^'Λ r ι ^*;? 1 rhe century (if 1 * Lichtti ι 1 ar) ι "/) j · > rt im uj ι _t υ ^Ί

ι ι

I It

i I

ill

I _- I f II 'f ₄ I (

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I ι

V tin HO

I nt ι -

r ". "■

; J0; 1

i.ä.t; cai, ck '

rs R u '' ;. ■

i: c iiiat i:

r; _f: i; 2 ι · ■ "\ _e: chichfc" ■ ':; ,, there,' ::::.

■ -yri b "tiki: ::> η erαa, itaη we : ί

"": '·, "E:?; 1 e ι ■ el an, a tin t er i ti e η i, „. i "

„„ ■ ■ ^ I, ι c. „Ir ::,„ „i: be 1 1, c ht et ,, d ο e ::, .. ί; η

. t i. \ 9 \ (I. 6

spectral composition of 'the absorption range of the light-absorbing dye used corresponds, by a test object passes, it vie commonly used for the quantitative testing of materials for \ production of shadow masks for ■ microelectronics is used and from lines with a reiteration between ■ 1 and 20 Microns, which are separated by equally wide spaces. The exposure level is such that the blackening in the transparent areas of the generated images, which correspond to the white lines of the test object, is limited * to the fog value. '' /

After exposure, the two plate materials are reversed under completely identical conditions at 20 ° C processed.

For this purpose, the exposed materials are first about 5 minutes and developed at pH 10.5 in the following developer liquid: - ""

Hydroquinone 2 g

Monomethyl p-aminophenol hemisulfate. 4- g potassium bromide '2 g ^:

Sodium carbonate ^ 40 g

Sodium sulfite 40 g

Potassium thiocyanate 5g

Water to make up to 1 liter

The materials are then treated in "a bleach bath" of the following composition for about 5 minutes:

Potassium dichromate . 5g !

strong sulfuric acid (d = 1.85) 10 ml!

Water to fill up "to 1000 ml,

After a few minutes of rinsing in water, the materials will;

Treated for 5 minutes in a clarifying bath of the following composition: Sodium sulfite. 100 g

Water to. Fill up to 1000 ral <

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After they have been rinsed in water for a few more minutes, the materials are evenly post-exposed in order to make the high-quality silver bromide developable. This is followed by a few minutes ' treatment in the following developer bath:' ^ Hydroquinone 5 6

f Monomethyl-p-amino'phenol-hemieuifat 1g Sodium sulfite ■. . ■ 40 g

Sodium. '50 6

Potassium bromide 0.5 g

Water to fill up to 1000 ml

The materials are then rinsed and dried.

The results clearly show that, in comparison to material B, material A without a compound according to the invention Has image distortion, especially where lines of 10 to 20 microns are reproduced, and also is inferior in terms of yellowness and edge sharpness.

Example 2 "

Example 1 is repeated with the difference that materials A and B are processed in such a way that one can use a developer liquid of the following composition is given a negative image:

Water ■ 800 ml

Monomethyl-p-aminophenol hemixulsfate 1.5 anhydrous sodium sulfite 25 g

Hydroquinone 6 g

anhydrous sodium carbonate 4-0 g

Potassium bromide 1 g

Water to fill up to -1 liter

Compared to material A, material B shows better image sharpness and less distortion in line reproduction.

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Claims (9)

Claims' 1. A silver halide photographic emulsion characterized by comprising a compound of the following general Formula contains: OR -OR in which: R is hydrogen, acyl, Hatogaiaeyl or acyl with a quater- nary ammonium group, R ^. Hydrogen, alkyl, aryl, halogen or alkoxy, and Rp is an aliphatic, aromatic or heterocyclic group. 2. Photographic silver halide emulsion according to claim 1, characterized in that in the formula jRo is a 1-substituted 5-tetrazolyl or 3-triazolyl group, or a 2-benzthiazolyl group represents. 3 · Photographic silver halide emulsion according to claim 1 or 2, characterized in that it is a Lippmann emulsion with an average grain size of \ ^ enisscr than 100 nm. * 4. Photographic emulsion according to claim 3> characterized in that the compound is present in a crowd! which is between 20 mg and 2 g per mole of silver halide. 5. Photographic emulsion according to claim 3 or 4, characterized in that characterized that the ratio of the silver halide} to the hydrophilic, colloidal binder between 1: 2 and! 4: 1. 6. Photographic emulsion according to any one of claims 3 to 5) characterized in that it is a silver bromide emulsion with a silborjoflid content of at most 8 MoI- ^ and one average grain size of h'dchsbens 80 nm. GV.580. , ' 309820/1056 7. Photographic ;: material characterized in that he. a carrier and an emulsion according to any one of claims 1 to 6. 8. Fhofcoßraphischea material according to claim 7r characterized that the wearer eats a glass slide. 9. A compound, r'.Le characterized by the following formula: is : -OR in which: R is hydrogen, acyl, haloacyl or acyl with a qimternüreri Ammonium group and. R _{0 is} a heterocycle. solder connection according to claim 9 »characterized in that R is hydrogen and R ^ is a 1-substituted 5-tetrazolyl or 3-triazclyl group or a 2-benzthiazolyl group. GV.58O ORIGINAL CONSTRUCTION 309820/1056