DE2227262A1 - PROCESS FOR DEVELOPING HIGH-CONTRAST PHOTOGRAPHIC ELEMENTS FOR USE IN THE PRINTING INDUSTRY - Google Patents

Description

PATENT ANWXLTE

DR. E. WIEGAND DIPL-ING. W. NIEMANN DR. M. KÖHLER DIPL-ING- C. GERNHARDT

MÖNCHEN HAMBURG

TELEPHONE: 55 5476 TELEGRAMS: CARPATENT

8000 MDNCHEN 15,

NUSSBAUMSTRASSE 10

5th June 1972

V. 41178/72 - Ko / Ne

• I'uji Photo PiIm Co., Ltd. riinami Ashigara-Shi, Kanagawa (Japan)

Process for developing high-contrast, photographic Elements for use in the graphic arts industry

The invention "deals with a developer composition for use in photographic materials for the graphic arts industry which contain a dihydroxybenzene developer and has at least one phenolic compound of the following general formula:

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where R., R ~, ^ z » ^E y, ^un ^ - ^ 5» ^ ^{e can be the} same or different, in each case a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, an alkoxyl group, a COOM group, in which M represents a hydrogen atom, a water-soluble cation or a hydrocarbon group, a SOJl group in which M has the meaning given above, a halogen atom, a β-R group in which R represents a hydrocarbon group or a substituted hydrocarbon group, a COR ¹ - Group in which R ^{1 represents} a hydrogen atom, a hydrocarbon group or a substituted hydrocarbon group or the grouping NR ¹¹ R ¹ ″ in which R ″ and R ″ ¹ each represent a hydrogen atom, a hydrocarbon radical or a substituted hydrocarbon radical.

The invention relates to a method of processing a high contrast photographic element for Use in the graphic industry. In particular, the invention relates to a method for developing high-contrast, photographic elements by processing a dot-like, high contrast photographic element for the graphic arts industry with a photographic emulsion layer greater than 80 mole percent is preferred contains more than 85 mol%, silver chloride, with a developer solution, which contains a sterically hindered phenol.

An object of the invention is a developing method for a high contrast photographic one Element while achieving good dot quality and at the same time consists of a development process that is in the Is able to produce elements for the graphic industry with good dot image quality over a long period of time, indeiu y £ uft oxidati on of an infectious developer solution is prevented.

2 U 9 8 8 2 /: 0 9 9 p

Line and halftone photographic reproductions are made carried out by, a silver halide photographic element high contrast or litho type image by image through a hatched screen or contrast screen exposed and then developed with a developer, producing continuous tone images in photographic Line and halftone (dot) images can be converted

It is most expedient if the line and point images consist of only one part of maximum density and one Background are constructed with a minimal density. However, it is a high contrast photographic element has the property of allocating a part of medium density besides a part of maximum density and the background form, a part always forms around the point spreads medium density, referred to as ingress or fringe (interference). The formation of interference is for the graphic industry is not cheap, as it uses point, q ualities are insured.

It is known in the art that interference is caused by the use of what is known as an infectious developer composition which essentially comprises a dihydroxybenzene type developer and a small amount Contains sulfite ions. A dihydroxybenzene-type developer, for example Hydroquinone, converted to quinone during the development process, and the quinone obtained reacts with Sodium sulfite with the formation of sodium hydroquinone monosulfonate. However, sodium hydroquinone monosulfonate is less reductive than hydroquinone because of its low level Electrode potential and is therefore · practically not in the Able to act as a developer. Therefore, the progress of development is not rapid, so that a

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Forms interference fringes or fringes. In contrast to is used when an infectious developer is used the concentration of free sulfite ions is kept at a low concentration because sodium sulfite is present in a small amount is added and as it is with a compound with carbonyl groups, such as p-formaldehyde, the is incorporated into the infectious developer, reacts according to the following equation:

CH ₀ O + Na ₀ SO, + H ₀ O ^ ' CH ₀ O-NaHSO-, + NaOH

Because of this, it becomes part of the development process difficult for the quinone to react with sulphurous acid to form hydroquinone monosulphonic acid, and thereby the quinone concentration is increased. The quinone produced in this way and the original hydroquinone have an effect a disproportionation reaction and form semiquinone. The semiquinon reduces silver halide and becomes even due to its high development effectiveness in Quinone transferred. From YuIe in J. Frank Inst., 2J5g, p 221 (194-5) describes that rapid development is obtained by successively repeating this procedure, thus a development with a high gamma vert is achieved.

Although a sulfite as one of the preservatives known for a photographic developer composition it is necessary to lower the concentration of sulphite in order to obtain better line and point reproductions to obtain.

Infectious developer compositions of this type therefore have, in comparison with conventional photographic Schwarz-Veiss developers poor stability, and the life of the infectious developing composition is short. Consequently

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that, when infectious developing compositions are used continuously, images with a low contrast · and a honing interference received because of the development did not happen quickly. It has therefore been proposed to add an anti-oxidant other than sulphite, to improve stability. At -this attempt is it is already known to use ascorbic acid in a solution of an infectious devi ckl erai as se (British patent specification 928 390) to be added. However, ascorbic acid has a poor stability and therefore tends to decompose. In particular, ascorbic acid tends to decompose when Metal ions such as copper ions or iron ions are present in a developer solution. Furthermore, as a result, the solution to the development is not sufficient stabilized. In addition, it has the disadvantage that the development process is slowed down and that the dot quality is lowered when the ascorbic acid is added in a large amount.

It has recently been reported by the applicant that a hindered phenol gives better stabilizing effects than ascorbic acid. On the other hand, are obtained when the silver chloride content 80 ° / o is increased above in a photographic element, such advantages that the developer is working faster and with sound images. high contrast can be obtained. However, as described above, the increase in silver chloride is accompanied by such drawbacks that the reproducible area of a halftone image is narrowed and the tendency is particularly pronounced in an aged or exhausted developing solution. To eliminate these disadvantages described above, a sulfite can be effectively incorporated into the developer solution, but in this i'all at the same time the dot quality of the re-

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gave worsened.

It is an object of the invention to provide a method of making a high contrast element having an increased, reproducible halftone area, ie, a wide exposure area between 0% dot area and 100% dot area, and with rapid progression of high contrast tone development by treating a lithographic photosensitive material which has a photographic emulsion layer containing greater than 80% silver chloride with a developing solution containing a hindered phenol. In particular, the invention is also effective even in a developing solution which is stored or used for a long period of time because of the increased reproducible range.

Another object of the invention is to provide a photographic element of high contrast for the graphic arts industry to enable reproductions with stable quality over a long period of time Period by using a developer solution with highly stabilizing property.

Another object of the invention is to simplify the control and stability of the developing solution.

Another object of the invention is to control the amount of replenishment of a developer solution during development to belittle.

On the basis of numerous investigations to achieve the objectives of the invention described above, it has now been found that excellent dot quality is obtained and the stability of a developing solution is greatly improved ν can be achieved by using a high contrast photographic element suitable for the graphic arts industry, which has a photographic emulsion layer which

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contains more than 80%, preferably more than 85 % sirber chloride, is treated with an infectious developer solution "which has at least one phenol compound of the following general formula:

OH

wherein R., Ro ₅ . R ^ j R ^, and R ₁ -, which can be the same or different, each represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, an alkoxyl group, the grouping COOM, the grouping SO, M, where M is in the above groups Represents hydrogen atom, a water-soluble cationic group or a hydrocarbon group, a halogen atom, the group SR, in which R represents a hydrocarbon group or a substituted hydrocarbon group, the group COR ¹ , in which R ^{1 represents} a hydrogen atom, a hydrocarbon group or a substituted hydrocarbon group or the grouping NR "R"', where R "and R ¹ " each represent a hydrogen atom, a hydrocarbon group or a substituted hydrocarbon group and in which R., Rp, R- ,, R ^ and R, - cannot be hydrogen atoms at the same time.

In the above general formula, suitable hydrocarbon groups can be, for example, alkyl groups, Be aryl groups, aralkyl groups and allyl groups. Suitable substituted hydrocarbon groups can

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for example, aryl groups and aralkyl groups, the are substituted with, for example, alkyl groups, hydroxyl groups and / or halogen atoms. In general, everyone is any compound of the above general formula is suitable for use in accordance with the invention as long as it is a phenol. is which has the property of being sterically hindered to be. Suitable examples of the water-soluble cationic group M are an alkali salt such as a sodium salt, a potassium salt and an ammonium salt,

Typical examples of the compounds represented by the general formula described above are shown below listed by specifying the groups, although the compounds used in the present invention are not limited to these specific compounds.

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W. W. Ph Ph Ph Ph KN W- KN -_ OO KN Ph KN KN KN ω KN • - VO LC w W. W. HH
Ph ω HH
HH H Ph KN KN O Ü O O KN O HH Ph Ph H-] HH KN Ph KN KN ' "st O - O W. O Ph HH W. W. ° W. Ph i. ° O Ph O KN KN W. W. pT HH W. KN KN KN b KN KN KN O W. Ph do HH Ph KV KN O O W. O W. W. Ph ■ Ph W. W. KN KN CM O O HH
Ph Ph O Ph HH M. KN Ph Ph KN KN KN KN W. O • Ph HH
Ph Ph KN KN IfN O KN H H O O O W. H-] O HH
HH HH W. Ph pi O ο · CM LOi O O H idung i CM KN> = * U.N. VD O H • H f-4 C- ON H H CM KN ¹ p H H H ο · '■ V

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• No. ^E l R ₂ ^R 3 ^R 4 ^R 5 17th CH ₅ H CH ₅ CH ₅ CH ₅ 18th ^ CH ₅ CH ₅ H CH ₅ CH ₅ 19th CH ₅ CH ₅ CH ₅ CH ₅ CH ₅ 20th C ₂ H ₅ H ' - H H H . 21 H H H ■ ^C 2 ^H * 5 H ' 22nd H E. C ₂ H ₅ H H 23 Yes-C ₅ H ₇ H ' H H H 24 H H H ■ * nC ₅ H ₇ H 25th • H E J! - ₅ η H H 26th ISO-C ₃ H ₇ H H H· H 27 .H ■ H H IsO-C ₅ H ₇ H : .V 28 H H ISO-C ₅ H ₇ H H 29 H ' ISO-C ₅ H ₇ H CH ₅ H 30th CH ₅ . H H H IsO-C ₅ H ₇ 31 iso-C, H ₇ CH :, CH, H H J I j j 32 ISO-C ₅ H ₇ ΟρΗς H H

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pi HH M. W. W. W. W. CJN - CJN K f W. W. M- ίτ! Hq HH W. HH W. - CJN
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pi W. W. W. W. -P Nt W. I. O O | t { O C- W * I. I. I. CJN φ KN KN • st O W. -P «Φ CQ pi O jt! O <D Yyh O O I. CQ I. I. O Ö ' -P O CQ co Ph ■ H ΚΛ KN • Η C- W. Kt-I
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Ö te KN ^ J- IXN C-. co U.N. C- in - KN KN KN KN "Nt «Φ

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No. CH ₃ H ^Λ R ₃ . ^{: R} A ^R 5 49 'η-Ό ₄ Η ₉ H "0-C ₄ H ₉ H H 50 ISO-C ₄ H ₉ H CH ₃ H H 51 SeC-C ₄ H ₉ H CH ₃ H H 52 ^ -C ₄ H ₉ . H CH ₃ H H 53 HC ₄ H ₉ CH ₃ \ j Xl *? H · ■ H · 54 ISO-C ₄ H ₉ CH ₃ CH ₃ H H 55 SeC-C ₄ H ₉ CH ₃ CH ₃ H H 56 TC ₄ H ₉ CH ₃ CH ₃ .. H H 57 ^ -C ₄ H ₉ C ₂ H ₅ CH ₃ H H 58 tC ₄ H ₉ CH, '
j CH ₃ H • H . 59 J-. ΓΙ TJ * H ISO-C ₃ H ₇ H H • < ⁶⁰ TC ₄ H ₉ TC ₄ H ₉ TC ₄ H ₉ H H '"' 6I ^ C ₄ H ₉ TC ₄ H ₉ H H H 62 tC ₄ H ₉ CH ₃ CH ₃ ' H H. 63 tC ₄ H ₉ H TC ₄ H ₉ H H 64 -C ₄ H ₉ H H

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■ No. * - ^σ 4 ^Η ₉ R ₂ R ₃ R ₄ ^R 5 65 ^ -C ₄ H ₉ H ISO-C ₄ H ₉ H H 66 ^ -C ₄ H ₉ H ■ SeC-C ₄ H ₉ H ' H 67 ISO-C ₃ H ₇ iso-C, H ₇ • ^ -C ₄ H ₉ H H 68 tC ₄ H ₉ tC ₄ H ₉ . tC ₄ H ₉ H H 69 . ^t - ^C 4 ^H 9 -C ₄ H ₉ C ₂ H ₅ H * ■ H 70 tC ₄ H ₉ 'tC ₄ H ₉ ISO-C ₃ H ₇ H ' H 71 '- ^ -C ₄ H ₉ tC ₄ H ₉ tC ₄ H ₉ H H 72 ^t -. ^C 4 ^fi 9 CH ₃ tC ₄ H ₉ - CH ₃ H 73 H . H tC ₄ H ₉ CH ₃ ' H 74 tC ₆ H ₁₃ H ■. ■ ^t " ^C 5 ^H ll H ■ H 75 H H CH ₃ H H •> 76 ^t " ^C 8 ^H 17 H tC ₈ H ₁₇ H H 77 H H CH ₃ H H 78 · H H CH ₂ CH = CH ₂ H H _'79 OCH ₃ ' H H H 80 H H H H

O CO 03 CO ro

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. Mr. R ₁ R ₂ R ₃ . ' ^R A ^R 5 81. H H H OCH ₃ H 82 ' H H OCH ₃ H H 83 OCH ₃ OCH ₃ H H . H 84 ■ fc-C ₄ H ₉ H OCH ₃ H H 85 H H H H 86 H H COOH H H * 87 H H . COOH H H 88 ' CH ₃ COOH H H H 89 H COOH H CH ₃ H 90 CH ₃ H COOH ■ H H 91 * -C ₄ H ₉ COOH H H 92
A. * -C ₄ H ₉ ^ C ₄ H ₉ CH ₂ CH ₂ COOH H H 93 H H Cl H H 94 · Cl Cl Cl H .H 95 H H Cl CH ₃ CH ₃ 96 H . H CH ₀ OH F. H

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ω w M. O ■ M. M. {XJ H "<
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M.
O V cn W. - O W. W. O OJ O H Vh
Ph W. W. O W. H O M. M. tr HH
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»■ Μ cn I. Vh O W. OJ cn W. -P O O vl- HH O CQ OJ O O I. vj- O K. O h-j ■ P in Ph ^- I. -P O I. - ^ H ₁ - cn i tO -P I. cn -P O W. W. CTi cn -P [Tj cn I. ^ h - o OJ W. -P O ω HH vh W. O O Vh I. tf> O i-t O Ό O O I. O O vh -P O Ph I. ι H -P I. i O CQ O -P CO. -P -P -P H ITv H W) Cn H O . I t ι C- cn O CM tCv H E- • Η Η CT * cn H O O O O H H H H Q)

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No. * ^R l R ₂ I. ^R 3 ^R 4 ' R ₅ Ill t H H t
I. H NH (CH ₂ ) ₄ SO ₃ H H 112 Br Br I.
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^J , NH ₀
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CH ₂ CHCOOH H . H 113 iso- H H I.
. I. H N (CH ₃ ) ₂ H 114 H H I. H 'NHC ₃ H ₇ H 115 H H ί
I. H JSHCOCH, H 116 H H I. H NHC ₂ H ₄ COCH ₃ H HO _t _ _c 117 -C ₄ H ₉ / ΤΓΤ // \\
—L> tip— </ y j CH ₃ H ' H -C ₄ H ₉ tC .E ₉ ■ / ~ ^C 4 ^H 9 H H OSO-C, By 119 H H 1
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I. I. \ O -P -P -P LjT 1 I. CM pi η H (XY O> CM CM CM O H H
/. '1 1 O O -P I I ^ JL ι] ■ ο CM CM CM H ttj O I. H f4 a Ö ö · U ■ ω

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No. ^R l "ho ■ R ₂ • 3 3 R ₃ R ₄ ■ ■ H R ₅ ^CH 2-Ö ^H0 tC H '
\ y ^W 4 9 . 123 ^a tC ₄ H ₉ H -CH-Q. Cl H H CH ₃ CH, 3
j 124. H H 125 H •
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W. • J. he" ■ ω O W. Λ pi O - O ο W. ■ Η pi I. O u l) I. ¹ O ß pp I W - O O
I. W. —Ο— ο O O - • J- O CM I. W. pi O H
pi CQ • Η Jk IJ VD t- ί CM
H CM
H ι W) CO CM
H Oil

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pi Ph W. H co
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I O pi _M. O m cn
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2227267

ρΓ teP
O cn to ^ CM
- Ο O to • ο pi -P O H J ll to
pi ω iw
W CM
O O ■ P. I.
'Til cn
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The above compounds are all known and are described in N. M. Emanuel and Yu N. Lyaskovskaya - The Inhibition of Fat Oxidation Process, published by Pergamon Press Ltd., 1967 and G. Scott - Atmospheric Oxidation and Antioxidation, published by Elsevier Publication Co., 1965, and they are also commercially available.

On the basis of extensive studies available, it has been found that the above general The compounds shown in the formula can significantly improve the preservation properties of a developing solution can, and in particular, xirenn a lithographic, light-sensitive material having a photographic emulsion layer containing more than 80 mol% bilber chloride contains, in the infectious developer solution, containing the above-described compound can be treated with an excellent photographic image excellent dot quality and less stripes or interference are formed.

When the lithographic photosensitive material of the type described above is in an infectious developing solution, which contains the compound of the general formula described above, is treated Halftone reproduction area not narrowed the appearance, making the reproducible halftone area will not be concentrated even in a developing solution which is stored or used for a long period of time, and printing plates can be made that have an increased halftone display area exhibit.

According to the method of the invention described above, dot type printing plates can be used for a long period of time and the control and preservation of the developing solution are facilitated.

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All of the compounds represented by the general formula are suitable for improving the preservation properties of an infectious developer solution, however, among them are the compounds represented by a general formula having at least one alkyl group as a substituent particularly effective, and also compounds having an alkyl group of a larger number of carbon atoms are more effective, for example, up to about 10 carbon atoms, preferably up to about 5 carbon atoms. Further are compounds of the general formula with one or two alkyl groups as substituents in the o-positions of the benzene ring to the hydroxyl group is particularly effective, and among them the hindered phenol is the The above general formula, which is represented by at least one alkyl group with a large steric hindrance, e.g. B. an isopropyl group, a tert-butyl group and a tert-amyl group, is substituted. Quite particularly favorable. Furthermore, it is also advantageous to use groups which differ from the alkyl group as substituents, such as, for example a sulfonic acid group, a carboxylic acid group and a Hydroxy alkyl group, to be introduced into the sterically hindered phenol in order to increase the water solubility of the compound.

An infectious developer is basically made up of a dihydroxybenzene (developer), a Alkali, a small amount of sulfite and optionally a sulfite ion buffer built up. The infectious developer of the invention further contains the above-mentioned hindered phenol,

Dihydroxybenzenes are known in the art and can easily be selected by those skilled in the art. Typical examples of these compounds are hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone,

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Toluhyd.roch.inone, methylhydroquinone. 1,3-dichlorohydro-

quinone, 2,5-dimethylhydroquinone and the like. Of these de-

preferred
For curlers, hydroquinone can be put to practical use.

These developers are used individually or in combination. A suitable amount of developer to be added is in the range from about 5 to 50 g, preferably et \ ^ a 10 to JO g per liter of developer.

A sulfite ion buffer can be used in such an amount that the sulfite concentration is low Value is held in the developer. Examples of these buffers are an aldehyde-alkali hydrogen sulfite addition product, such as formalin sodium hydrogen sulfite, a ketone-alkali hydrogen sulfite addition product such as for example acetone-sodium hydrogen sulfite addition product and a carbonyl bisulfite-amine condensation product, such as sodium bis (2-hydroxyethyl) aminomethanesulfonate. The sulfite ion buffer is not on the The above examples are limited and each component of the addition product or condensation product can be used by the developer can be added. The amount of sulfite ion buffer added can range from about 13 to 150 grams, preferably JO up to 60 g, per "liter of developer.

An alkali is added to strengthen the developer to an alkaline range, preferably a pH above 8 preferably to a pH of 9 to 11. Consequently, the addition amount and the type of addition can be freely selected and are not limited to the above examples limited.

The developer solution can also contain a pH buffer such as an alkanolamine, a water soluble acid, e.g. B. acetic acid, boric acid, an alkali, e.g. B. sodium hydroxide, or a salt, e.g. B. sodium carbonate. Furthermore, it can be an alkali halide as

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contain a development regulator. It can also be an organic anti-fogging agent in some cases, z. B. benzotriazole, i-phenyl-iJ-mercapto-tetrazole) Polyalkylene oxide, an amine and an organic solvent, e.g. B. triethylene glycol, dimethylformamide, methanol, Cellosolve, in an amount from 0 to about 300 ml per liter contained in the developing solution.

As described above, one property of the infectious developing solution is that the concentration of free sulfite is low. For this purpose, a sulfite ion buffer material, such as For example, formaldehyde-sodium bisulfite adduct is used.

In general, the concentration of free sulfite ions by adding an alkali sulfite, such as Sodium sulfite, in an amount not exceeding 5 g Ο © 1 liter of the developer solution together with regulated by a sulfite ion buffer agent. Sulphite is generally used in an amount not exceeding 1 g per liter is added to the developing solution, and this increases the stability of the developing solution is somewhat improved, although the dot quality is more or less reduced. However, as described above, this level of stability is generally unsatisfactory. Ogel Although the compounds of the invention have the inherent poor stability of an infectious developing solution, which does not contain any of a sulfite ion buffering agent such as a formaldehyde-sodium bisulfite adduct, improve to a certain extent, they significantly increase the stability of an infectious developer solution, both an alkali sulfite in an amount of not more than 5 g ü'e liter of the developer solution (0.005 "to 0.05 Hol contains free sulfite) and a sulfite ion buffer. I. E. , The phenols of the invention exert an effect by themselves in a developer solution that does not contain free sulfite

209882 / Π99S

contains, for example, a developer solution that does not contain any sulphite other than formaldehyde-bisulphite adduct, however, this effect is very small. Therefore, from a practical point of view, the invention can on best to be applied in a developer solution that contains a small amount of free sulfite. A single phenol of the invention or a combination of two or more phenols of the invention can be employed. The amount of phenols to be added to the developer solution of the invention varies depending on the composition of the Developer solution and the types of phenols used, however, the amount used will generally be within the range from about 2 mg to 20 g per liter of developer solution, more preferably from about 10 mg to 5 g per liter of developer solution. The sterically hindered phenol of the general formula described above is generally converted into an infectious one Developer solution incorporated in the preparation of the developer solution. If the developing solution is provisionally saved as concentrated liquids or powdery components and are mixed, diluted or dissolved in water when used, it is advantageous to the phenol described above into one of the concentrated liquids or powdered ingredients to incorporate. In particular, the use of liquid developer compositions is advantageous because in such a case The stability of the liquid developer composition can be significantly improved by previously using the phenol of the above general formula is incorporated into the liquid developer compound. Generally it is a liquid one

Developer compound made up of two liquid components, one comprising the developer and the other comprising the alkaline component. In such a case it can hindered phenol can be incorporated in each part; however, it is more beneficial to have the phenol in the part

209882/0 99 p

incorporate that contains the developer, eliminating the entire liquid developer! as se excellent stability receives. In addition, the developer solution is produced by "diluting the liquid developer compound." was also excellent stability.

Solvents such as water, benzyl alcohol, ethylene glycol, Diethylene glycol, triethylene glycol, glacial acetic acid or a combination of these solvents can be used. It is also possible to change the stability of the developer solution to improve by the phenols of the invention in the course of development or after the development of the photographic Materials to be added to the print.

The lithographic photosensitive material to be treated in the process of the invention is a photosensitive material having a photographic emulsion layer containing more than 80 mol% of silver chloride, that is, a silver chloride emulsion layer, a silver chlorobromide emulsion layer or a silver chloroiodobromide emulsion layer, each contains more than 80 % silver chloride. The binder in which the silver halide is dispersed is a hydrophilic polymer including gelatin, a gelatin derivative such as phthalate gelatin and malonate gelatin, a cellulose derivative such as hydroxyethyl cellulose and carboxymethyl cellulose, a water-soluble starch such as dextrin, and alkali starch or hydrophilic polymers such as polyvinyl alcohol, polyvinylpyrrolidone and polystyrene sulfonic acid. The photosensitive material used according to the invention can also contain * a hydrophobic polymer, e.g. a polyalkylacrylate and a gelatin plasticizer such as glycerol and trimetlianolpropane.

The photosensitive for the photosensitive to be treated according to the invention Material used in emulsion can be made by various methods during its manufacture or before be made sensitive to coating. For example, the emulsion can be prepared using known chemical Sensitization methods are sensitized, for example by. Sodium thiosulfate, an alkyl thiourea, a gold compound such as a complex salt of monovalent gold and thiocyanic acid or mixtures these methods. The emulsion can also contain a heavy metal compound, e.g. B. a connection of platinum, palladium, iridium, rhodium, cadmium and the like. Furthermore, the emulsion can be orthochromatic or panchromatic by adding a sensitizing dye, such as. B. a cyanine dye or a merocyanine dye, be sensitized.

In addition, the emulsion used according to the invention can contain agents to improve the dot quality, such as a polyalkylene oxide and an amine compound (cf. US Pat. No. 3,288,612, DOS 1 932 882 and US Pat. No. J 345 175) or sodium benzene thiosulfate, benzotriazole or a 3 ₅ 3a ~ 7-tetrazaindene derivative (cf. US Pat. No. 3,375,114 and US Pat. No. 3,333,959)

Emulsion containing a hardening agent, e.g. B. formaldehyde, Hesorcinol dialdehyde, dimethylolurea, 2,4-dichloro-6-hydroxy-1,3,5-triazine (see U.S. Patent 3,325,287) and mucochloric acid. The emulsion may also contain a surfactant, e.g. B. Saponin to the application of the To facilitate emulsion. The emulsion can also be a modifier for the progress of development such as a 3-pyrazolidone derivative and a pyrazolone derivative, and may further contain a development accelerator contain, such as a quaternary ammonium salt and a cationic, upper-

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surface active agents. As a support for the photosensitive "treated" according to the process according to the invention Materials are, for example, a glass plate, cellulose acetate, polystyrene, polycarbonate, polyethylene terephthalate and the like.

The invention will now be described in detail on the basis of the following Examples explained »

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Example 1

A lithographiachea light-sensitive material having a photographiachen Emulaionsachicht, the # 86 mol silver chloride, silver iodide 0.2 mol # and contains as reat silver bromide, was exposed to a suspension wedge for Senaitometrie by a Magentakontaktsieb with 150 lines and then at 20 ⁰ C in one of the developed three types of developer solutions A, B and C of the respective compositions listed below. For comparison, a lithographic photosensitive material having a photographic emulsion layer containing 72 mol% silver chloride, 0.2 mol% silver iodide and the balance silver bromide was exposed as above and then similarly subjected to one of the three types of processing described above 20 ⁰ C developed.

Development solution A:

Sodium carbonate monohydrate 50 g

Formaldehyde-sodium hydrogen sulfite addition product 45 g

Sodium bromide 2 g

Hydroquinone 18 g

Sodium sulfite 2 g

Water supplemented to a total volume of 1 1

Developer solution B:

1.0 g of the above-described compound 2 was added to the developer solution A.

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Developer solution G;

3 g of sodium sulfite were added to the developer solution A admitted.

The photographic properties obtained are shown in the following table.

in the (III) Tabel I ' (JIl (VII) (viii). J (ii) LH II (ti 39 a no (g7it (lake) 8th 10 100 34 7th A. b no 170 8th 13th 100 90 7th A. a link - 180 10 13th 100 85 9 B. b link 2 1.0 170 8th 13th 100 7th B. 2 1.0- 180

C a sodium sulfite 3.0 195 4 14 100 65 C b sodium sulfite 3.0 200 3 14 100 60

(I): developing solution

(II): light-sensitive material used (III): additive in the developer solution (IV): amount of additive

(V): Development time (VI): Dot quality (VII): Number of steps of the semitone

(VIII): Sensitivity (i) fresh / (ii) after passage of time (IX): dot quality obtained using the developing solution with the lapse of time

Further, the photosensitive material indicated by (a) in the above table was a lithographic one light-sensitive material having a photographic emulsion layer comprising 86 mol- # silver chloride, 0.2 mol- # Contained silver iodide and the remainder silver bromide, and that

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The photosensitive material indicated by (b) was a lithographic photosensitive material having a photographic emulsion layer containing 72 molar silver chloride, 0.2 molar silver iodide and the balance silver bromide. The developing time was selected so that the sensitivity of the photosensitive material developed during the period became the sensitivity of the lithographic photosensitive material (a) obtained when the photosensitive material was developed in the developing solution (A) for 170 seconds (this sensitivity became defined as 100). Purikt quality was expressed by a progressive scale of 10 units, where "10" was very good and "1" was very poor. The Halbtonstufenzahl was the stage number from 0 ° / o to 100 $ in dot area percentage data, when the photosensitive material was exposed to a step wedge with a difusen light density of 0.1 and then a contact screen was stacked and thus the larger the stage number was, the greater the reproducible halftone . After the lapse of time, the developer solution was a developer solution with a volume of 500 ml, which was broken down by aerating in a developer dish of 20 × 25 cm for 5 hours. As shown in Table I, the developer solution (A), which did not contain the hindered phenol represented by the general formula given above, was greatly reduced in sensitivity when aerated during the 5 hour period.

For comparison purposes, the developer solution (C), containing 3.0 g of sodium sulfite in place of Compound 2 in the invention, was used, but although the Decrease in sensitivity when the developing solution

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5 hours was ventilated, was less than in the Pail der
Developer solution A, the degradation of the developer solution was very pronounced and also in the case of using the developer solution O, the image quality obtained was poor,
even if the developing solution was fresh. On the other hand, the developing solution containing 1.0 g of Compound 2 showed the least reduction in sensitivity when it was used under the above conditions
has been ventilated. In particular, when the light-sensitive material (a) was treated with the photographic emulsion layer containing 36 mol- ^ silver chloride in the developing solution (B), the dot quality was quite excellent. In this pail, the reproducible halftone area was not narrowed and an enlarged reproducible halftone area was also obtained even when the developing solution was used during one
has been ventilated for a long period of time. Thus, when the photosensitive materials (a) were treated in the developing solution (B), excellent printing plates which were durable for a long period of time were obtained.

Example 2

A silver halide emulsion having a silver halide composition of $ 90 silver chloride, $ 0.2 mol
Silver iodide and the balance silver bromide were subjected to gold sensitization and sulfur sensitization and then optically sensitized using 3-carboxymethyl-5- / 2- (3-ethylthiazolinylidene) ethylidene-7-rhodanine. Then polyoxyethylene nonylphenyl ether containing 50 ethylene oxide groups and the development accelerator

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.34-22272B2

C ₂ H ₅

NCH ₂ CH ₂ CH ₂ Ch-NHCONH CH,

(described in the published Japanese patent application 23 465/1965) added to the emulsion, and mucochloric acid was further added. Then, after polybutyl methacrylate was added, the The resulting emulsion was applied to a film base to obtain a lithographic photosensitive film became. A lithographic one was also used for comparison photosensitive film using a silver halide emulsion containing 75 mol # silver chloride, 0.2 mol% silver iodide and the remainder silver bromide, manufactured.

The lithographic light-sensitive films prepared above were subjected to wedge exposure for sensitometry through a Magentakontaktsieb with 150 lines and then treated at 20 ⁰ C in one of the two developing solutions of the following compositions:

Developer solution D; Solution I:

distilled water triethylene glycol

Formaldehyde-sodium hydrogen sulfite addition product Hydroquinone sodium sulfite

distilled water supplemented to a total volume of 125 ml

60 ml 30th ml 45 G 16 G 2 S.

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solution II:

distilled water 80 ml

Sodium carbonate monohydrate 30 g

Sodium hydroxide 5 g

Boric acid - 3 g

Sodium bromide 2g

distilled water supplemented to a total volume of 125 ml

In use, 750 ml of water was added to solution I and then solution II became to form of 1 1 developer solution added.

Developer solution E:

This developer solution was prepared by adding 0.5 g of the above-mentioned compound 92 to the Solution I of developer solution D and subsequent mixing of solution I and solution II prepared.

The photographic properties thus obtained are shown in the following table.

in illl you) (iy) , ill ill! (πι)

(g / l) (sec)

D c none - 120 8 10 100 35 5

D d none - 180 8 - 13 100 -35 5

E c connection 92 0.5 170 10 13 100 95 9

E d connection 92 0.5 180 8 13 100 88 7

The column heads (I) to (IX) have the same meaning as in Table I.

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In the table above, that was photosensitive Material (c) a light-sensitive material having a photographic emulsion layer containing 90 M0I-9S silver chloride and the light-sensitive material (d) was a light-sensitive material having a photographic Emulsion layer, the 75 Mo1- $ silver chloride contained.

As can be seen from the results shown in Table II, the developing solution showed the Compound 92 contained excellent preservation properties, and particularly when the lithographic photosensitive PiIm with a photographic emulsion layer, which contained 90 mole # silver chloride in the When developing solution was treated, excellent dot quality was obtained in the fresh solution and even in the developing solution which had been aerated for a long period of time, there was the one obtained Point quality also excellent.

Example 3 Developer solution F:

Sodium carbonate monohydrate 40 g

Forraaldehyde-sodium hydrogen sulfite addition product 60 g

Potassium bromide 2 g

Boric acid 6 g

Hydroquinone 18 g

Sodium sulfite 2 g

Water replenished to a total volume
from 1 1

Developer solutions G, H, I, J, K, L and M:

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These developer solutions were made by adding
of compounds 1, 3, 4, 5, 6, 7 or 8 to the developer solution ^{J 1.}

The lithographic photosensitive film with
a photographic emulsion layer containing 95 moles
Silver chloride, 0.1 mol # silver iodide and the remainder SiI berbromid (photosensitive material (s)) contained
and the comparative photosensitive material (f) with
a photographic emulsion layer which is $ 75 mole
Containing silver chloride was treated in one of these developing solutions. The results obtained are
listed in the table below.

Table III

HU . (HD (IV) Ul (VI) (VIP (VHI) (IX)

(T) TTi) -

P e none 170 8 10 100 42 5

P f none - 180 8 13 100 40 5

G e connection 1 1.0 170 10 13 100 85 8

G f connection 1 1.0 180 8 13 100 83 6

H e connection 3- 1.5 170 10 13 100 90 9

H f connection 3 1.5 180 8 13 100 87 7

I e connection 4 2.0 170 10 13 100 95 9

I f connection 4 2.0 180 8 13 100 93 7

J e connection 5 1.0 170 10 13 100 80 8

J f connection 5 1.0 180 8 13 1QO 79 6

K e connection 6 2.0 170 10 13 100 85 8

K f connection 6 2.0 180 8 13 100 85 6

I e connection 7 1.5 170 10 13 100 88 9

I f connection 7 1.5 180 8 13 100 85 7

M e connection 8 0.5 170 10 13 100 90 9

M f connection 8 0.5 180 8 13 100 89 7

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The column heads (I) to (IX) in the above table have the same meaning as in table I.

How au ^r; As can be seen from the results shown in the table, the developing solutions containing the above-mentioned compounds of the invention showed excellent preservation properties, especially when the light-sensitive material was treated with a photographic emulsion layer containing 95 mol% of silver chloride in the developing solution obtained excellent dot quality. Likewise, when the light-sensitive material was treated in the developing solution, it gave excellent dot quality even after aeration for a long period of time.

Example 4 Developer solution N;

Sodium carbonate monohydrate 60 g

] formaldehyde-sodium hydrogen sulfite addition product 50 g

Potassium bromide 2 g

Boric acid 3 g

Hydroquinone 15 g

Sodium sulfite. 2 g

Water replenished to a total volume
from 11

Developer solution 0:

The developing solution was prepared by adding 1.0 g of the above compound 38 to the developing solution (N) manufactured.

A lithographic photosensitive material (g) having a photographic emulsion layer which is 92 $

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Silver chloride, 0.2 mole # silver iodide and the remainder Contained silver bromide and a lithographic light-sensitive material (h) with a photographic Emulsion layer containing 73 mol $ silver chloride, were in one of the above-described developing solutions using "an automatic developing treatment." treated. The results obtained are shown in the table below.

mi - Tabel (170 17th (71) (VII) (VIII) I. (U) [IX II (Ill) ill (i) 45 G - 8th 10 100 42 VJl N H no - 95 8th 13th 100 95 VJI N G no 1.0 100 10 13th 100 91 9 O H link 38 1.0 95 8th 13th 100 7th O link 38 100

The column heads (I) to (IX) in the above table have the same meaning as in table I. The developer solution after the lapse of time shown by (ii) in Table II, was that in an automatic processing processor was used for 24 hours at room temperature.

As can be seen from the results shown in Table IV, the above-described developing solution showed according to the invention excellent preservation properties, and especially when the photosensitive Material with the photographic emulsion layer containing 92 mol- $ silver chloride in the developing solution, containing the hindered phenol, became printing plates excellent in dot reproducibility obtain. Furthermore, the halftone reproduction range has not been narrowed, and even if the developer

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solution (0) was ventilated for a long period of time, a larger halftone reproduction area became and thus excellent printing plates could be produced after a long period of time.

8? / Fl995

Claims (1)

Claims 1. Infectious developing agent for use with Photographic materials for the graphic industry, characterized in that a dihydroxybenzene developer and at least one phenol compound represented by the following general formula where R ^, R ₂ , R ~, R. and R, -, which can be the same or different, each represent a hydrogen atom, a hydrocarbon group, a substituted hydrocarbon group, an alkoxyl group, the grouping COOM, in which M is a hydrogen atom, represents a water-soluble cation or a hydrocarbon group, an SO * M group in which M has the meaning given above, a halogen atom, an SR group in which R represents a hydrocarbon radical or a substituted hydrocarbon radical, the grouping COR ¹ , in R ^{1 represents} a hydrogen atom, a hydrocarbon radical or a substituted hydrocarbon radical, or the grouping NR ¹¹ R " ¹ , in which R" and R " ¹ each represent a hydrogen atom, a hydrocarbon radical or a substituted hydrocarbon radical. 2. developer composition according to claim 1, characterized in that the composition additionally contains an aldehyde-alkali bisulfite adduct, a ketone-alkali bisulfite adduct or 20 9RR? / 099 has a combination thereof. 3. developer composition according to claim 2, characterized in that the composition is a formaldehyde-sodium bisulfite adduct contains. 4. developer composition according to claim 1, characterized in that the dihydroxybenzene developer from Hydroquinone, chlorohydroquinone, bromohydroquinone, is opropy! Hydroquinone, Toluhydroquinone, Methy! Hydroquinone, 2,3-dichlorohydroquinone or 2,5-dimethylhydroquinone consists. 5 ' developer composition according to claim 4, characterized in that the dihydroxybenzene developer consists of hydroquinone. 6. developer composition according to claim 1, characterized in that the phenolic compound in an amount in the range of about 2 mg to 20 g per month of developer solution and wherein the dihydroxybenzene developer is present in an amount ranging from about 5 to 50 grams per liter Developer solution is present. 7. developer composition according to claim 1, characterized in that at least one of the radicals R ^, R2, R-z R, or R, - is an alkyl group. 8. developer composition according to claim 1, characterized in that one of the radicals R .. and R ₂ or both radicals R ₁ and R _{2 represent} alkyl groups. 9. developer composition according to claim 8, characterized in that the alkyl group is an isopropyl group, is a tertiary butyl group or a tertiary amyl group. 10. developer composition according to claim 7, characterized in that the phenolic compound is a sulfonic acid group, a carboxylic acid group or a hydroxyalkyl group as a substituent. 20 9 B ft? / 09-95 2227.26? Process for the production of photographic materials for the graphic industry, characterized in that, that a silver halide light-sensitive material having a photographic emulsion layer, that contains more than 80 mol $ silver chloride in an infectious developer solution that is a dihydroxy contains benzene developer and at least one phenolic compound of the following general formula: wherein R .., Rp> R- *, R ₄ and R ₁ -, which can be identical or different, each represent a hydrogen atom
Hydrocarbon radical, a substituted hydrocarbon radical, an alkoxyl radical, the group COOM, in which M represents a hydrogen atom, a water-soluble cation or a hydrocarbon group, the group SCzM, in which M has the meaning given above, a halogen atom, the group SR,
where R is a hydrocarbon radical or a substituted hydrocarbon radical, the grouping COR ¹ , where R 'is a hydrogen atom, a hydrocarbon radical or a substituted hydrocarbon radical or the grouping NR "R"' is,
wherein R "and R" ¹ each represent a hydrogen atom, a hydrocarbon radical or a substituted hydrocarbon radical. 209887/0995 12. The method according to claim 11, characterized in that at least one of the radicals R. |, Rg, R_, R. or Rf- is an alkyl group. 13. The method according to claim 11, characterized in that one of the radicals R .. and R ₂ or both radicals RJ and R _{2 are} alkyl radicals. 14. The method according to claim 13, characterized in that the alkyl radical is an isopropyl radical tert-butyl radical or a tert-amyl radical. 15. The method according to claim 12, characterized in that that a phenolic compound with a sulfonic acid group, a carboxylic acid group or a hydroxyalkyl group is used as a substituent. 16. The method according to claim 11, characterized in that the mass additionally free sulfite and an aldehyde-alkali bisulfite adduct, a ketone-alkali bisulfite adduct or a combination thereof. 17. The method according to claim 16, characterized in that that the mass is a formaldehyde-sodium bisulfite adduct contains. 18. The method according to claim 11, characterized in that the dihydroxybenzene developer is hydroquinone, Chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, Toluhydroquinone, methyl hydroquinone, 2,3-dichlorohydroquinone or 2,5-dimethylhydroquinone is used. 19. The method according to claim 18, characterized in that the dihydroxybenzene developer is hydroquinone is used. 20. The method according to claim 11, characterized in that that the phenolic compound in an amount ranging from about 2 mg to 20 liters of the developer solution and wherein the dihydroxybenzene developer is present in an amount ranging from about 5 to 50 grams per liter the developer solution is present. 209882/0995