DE2263808A1 - LIGHT SENSITIVE SILVER HALOGENIDE MATERIAL - Google Patents

Description

The invention relates to a silver halide photosensitive material, and more particularly to a lithographic material photosensitive material that provides an image with a high edge gradient.

If a blackened surface and an un-blackened surface abut on a photographic image, becomes the ratio of the change in optical density versus distance in a direction at right angles to the Tangent defined as edge gradient. In general, the higher the edge gradient, the sharper the image. In particular is a photosensitive material that can provide an image with a high edge gradient, for example as lithographic photosensitive material for use in photographic plate-making processes

309827/0882

bar, taking a point spread using a glass screen or a contact screen. To this photosensitive Developing materials so that an image with a high edge gradient is obtained becomes a specialty developer with a high pH, which has a hydroquinone as a developing agent and a small amount of sulfite (called "infectious Developer ") is used.

On the other hand, it is known that when a polyalkylene oxide derivative such as the addition polymer of 1 molecule of sorbitan monolaurate with about 20 molecules of ethylene oxide, used in a photosensitive material, an increase in contrast is caused.

However, has an emulsion in which a polyalkylene oxide derivative is used has the disadvantage that a prolonged development is required to obtain high contrast.

In addition, an emulsion containing a polyalkylene oxide derivative requires a long initial development before onset of the infectious development, such initial development after the infectious development starts being high Provides contrast by considerably enhancing the infectious development. Hence it is an extremely low one Contrast gradation obtained in the initial development coexists with a high contrast gradation, which leads to an inadequate "curve tail" or lower part of the curve (cf. FIG. 1, curve 11). This is due to the fact attributed that the polyalkylene oxide derivative is the onset point the infectious development with regard to the individual silver halide grains contained in the emulsion,

309827/0882

To the photosensitive material according to the invention the technique of spectral sensitization can be used. Most of the sensitizing dyes that are used for the spectral sensitization used, worsen the "curve tail piece" ("toe-gradation"), which also was the case when the aforementioned polyalkylene oxide derivatives were used. In these cases, even if a high contrast can be obtained in a half tone image becomes, good points with sharp edges with a relatively short-term development, as is usually practical is executed (less than 3 minutes) in the case of recording ■ tion of point spreadsheets cannot be obtained.

The object of the invention is therefore to create an emulsion that can be used to deliver high edge gradients using a relatively short development time is suitable. Another purpose of the invention is to provide an emulsion which to deliver points with a good slack or lower Area in the blackening curve, i.e. when plotting density against exposure (log E), the characteristic curve being continues in the region of decreasing exposure with constantly decreasing gradients to a point at which the Gradient becomes zero, that is, the curve becomes parallel and eventually coincides with log E-axis. The area at which a flattening of the curve begins is known in the art as a curve tail piece or lower part of the blackening curve or as The sag of the characteristic curve. A further purpose of the invention is to create an improvement or elimination of the Deterioration of the toe-gradation caused by the use of certain sensitizing dyes is caused without causing a decrease in photosensitivity while, on the other hand, an oversensitizing effect is created. Another purpose of the invention is to determine the size and quality of individual points in the density range, in which the spot size is small, to make uniform.

It has been found that the above-described purposes according to the invention can be achieved by using a photo-

309827/0882

used graphic silver halide emulsion, the at least one polyalkylene oxide derivative and, at least one compound of the general formula I below

(D

where Q contains those necessary to form a heterocyclic ring (which may optionally be substituted) Atoms and R is an alkyl group, aryl group or a heterocyclic group Represent group.

In Fig. 1 of the drawing, a characteristic curve is shown, with the optical density (D) on the vertical axis and the Exposure amount (log E) are plotted on the horizontal axis.

Figs. 2 to 5 show curves showing the relationship between the distance / E (unit: micron} 7 to the optical density in the Illustrate the edge part of a point.

In the general formula I given above,

the
tet Q are the atoms necessary to complete a heterocyclic ring (where the ring can be substituted) e.g. benzothiazoline-2-thione ring, 6-methyl-benzothiazoline-2-thione ring, 6-ethyl-benzothiazoline-2-thione ring, 6- Methoxy-benzothiazoline-2-thione ring, 6-chloro-benzothiazoline-2-thione ring, A, 5-tetramethylene thiazoline-2-thione ring, 4,5-trimethylene thiazoline-2-thione ring, naphthothiazoline-2-thione ring, thiazolidine-2-thione ring ( e.g. thiazolidine-2-thione ring, 4-methylthiazolidine-2-thione ring, etc.), imidazoline-2-thione ring (e.g. 1,5 ~ dimethylimidazolidine-2-thione ring, 1,3-diethylimidazolidine-2-thione ring, etc.), Selenazolidine-2-thione ring (e.g. selenazolidine-2-thione ring, 4-methylselenazolidine-2-thione ring, etc.), a 1,3,4-thiadiazoline-2-thione ring (e.g. 1,3,4-thiadiazoline-2-thione ring , 5-methyl-1,3,4-thiadiazoline-2-thione ring, 5-ethylthio-1,3,4-thiadiazoline-2-thione ring, 5- {2- (4-phenyl-5-thio-1,3 , 4-thiadiazolin-2-yl) mercaptoethylthio] -1,3,4-thiadiazolin-2-thione ring, etc.), 1,3,4-selenadiazolin-2-th ion ring (e.g. 1,3,4-selenadiazoline-2-thione ring,

309827/0882

5-ethyl-1,3,4-selenadiazoline-2-thione ring, etc.), 4-selenazoline-2-thione ring (e.g. 4-selenazoline-2-thione ring, 4-methyl-4-selenazoline-2-thione ring, 4-phenyl-4-selenazoline-2-thione ring, etc.), 1,2-dihydropyridine-2-thione ring (e.g. 1,2-dihydropyridine-2-thione ring, 6-ethyl-1,2-dihydropyridine-2-thione ring, etc.), benzoxazoline-2-thione ring (e.g. benzoxazoline-2-thione ring, 6-ethylbenzoxazoline-2-thione ring, 6-methoxybenzoxazoline-2-thione ring, 5-methylbenzoxazoline-2-thione ring, etc.), benzimidazoline-2-thione ring (e.g. 1,3-dimethylbenzimidazoline-2-thione ring, 1,3-di-n-propylbenzimidazoline-2-thione ring, 1 ^ -Di-n-decylbenzimidazoline ^ -thione ring, 1,3-dibenzylbenzimidazoline-2-thione ring, 5-chloro-1,3-dimethylbenzimidazoline ~ 2-thione ring, 5-methyl-1,3-di-benzylbenzimidazoline-2-thione ring etc.), benzoselenazoline-2-thione ring (e.g. benzoselenazoline-2-thione ring, 6-ethylbenzoselenazoline-2-thione ring, 6-methoxybenzoselenazoline-2-thione ring, 6-chlorobenzoselenazoline-2-thione ring, etc.), 1,2-dihydroquinoline-2-thione ring (e.g. 1,2-r-dihydroquinoline-2-thione ring, 6-methyl-1,2-dihydroquinoline-2-thione ring, 6-chloro-1 ^ -dihydroquinoline ^ -thione ring, etc.) or the like.

The group R lom includes an unsubstituted or with one Hydroxy, aryl, morpholino or a similar group Alkyl group with 1-13 carbon atoms, preferably 1-6 carbon atoms, e.g. methyl, ethyl, propyl, hexyl, decyl, hydroxyethyl, benzyl or morpholinoethyl group or the like; aryl group unsubstituted or substituted with an alkyl, alkoxy, halogen or similar group, e.g. phenyl, 2-methylphenyl, 4-methoxyphenyl or 4-chlorophenyl group or. like; heterocyclic ring groups such as 2-pyridyl group, dipyridyl group or the like

Specific examples of various preferred compounds used in accordance with the invention are given below:

309827/0882

(i-i)

(1-2)

CH.

: C = SF 9O ^Ü C

C = S

• Ν '

75 ⁰ C

(1-3)

(1-4)

11-C ₃ H ₇ 74 ⁰ C

= S 55 ⁰ C

309827/0882

(1-5)

= S

149 ⁰ C

= S 19O ° C

(1-7)

87 ⁰ C

(1-8)

= S 13O ⁰ C

309827/0882

(1-9) H ₂

C ₁ H,

C = S 8l ~ 82 ° C

(I-IO) Ho

C = S

2 CH.

102 ⁰ C

(1-11)

C = S

C ₂ H ₄ OH

(1-12)

CH.

'C =

N CH. 96 ⁰ C

^F 114 ⁰ C

309827/0882

(1-13)

H _n C ₀ OOC
2

CH

3. ^ -N

C = S F 162 ° C

(1-14)

CH.

C = S

82 ° C

(1-15)

CH

CH-

(1-16)

C = S

F 119 C

166 ° c

309827/0882

(1-17)

C £

F 113 ⁰ C

(1-18)

ι.

CH-,

133 ° F

(1-19)

C = S

^nC 3 ^H 7 92 ° C

(1-20)

Se.

N CH.

= ^c u

6o ° c

309827/0882

(1-21)

CH-

N _n .

C = S

N
CH-

'F

151 ° C

(1-22)

HC ₃ H ₇

C = S liquid

(1-23)

(1-24)

^η - ° 10 ^Η 21 N.

^ C = S

CH

HC ₁₀ H ₂₁

C = S

N

CHr

fluid

309827/0882

(1-25)

(1-26) CH-

(1-27)

(1-28)

CH,

• Ν,

■ Ν

I,

169 ° c

CH ₂

LC = S

CH ₂ -

143 ° C

118 ° C 184 ⁰ C.

309827/0882

(1-29)

- ΛΖ -

94 ⁰ C

(1-30)

(1-31)

F- -46 ° C

H ₂ C

HpC ²

C = S

CH ₂ -R 123 ° C

309827/0882

(1-33)

H ₂ CH ₂ C.

= S ^F 625 ⁰ C

CH-

(1-34)

^H 3 ^CS

'C =

.Ah.

(1-35)

H ₃ CS

= S

88 ⁰ C

108 ⁰ C

309827/0882

(1-36)

(1-37)

- 15- ™

'C =

66 ° C

^H 3 ^C

= S 152 ⁰ C

(1-38)

SC 2-SCH ₂ CH ₂ S

.S.

\ / r

C = S

N-N

N-N

145 ° C

(1-39)

173 ⁰ C

309827/0882

Although the compounds listed above can be synthesized according to conventionally known procedures, The following are synthesis examples of those listed above Connections indicated.

Synthesis example I (compounds 1-1 to 1-8)

These compounds can be prepared according to the procedure described in Journal of The Chemical Society, 1939, pp. 473-476 using 2-mercaptobenzonthiazole as a starting material.

Synthesis example II (compounds 1-9 to 1-17)

The compounds can be made according to the method described in The Journal of The Chemical Society, 1949, pages 1503-1509 by reacting dithiocarbamate with an oc-haloketone getting produced.

The compounds I-18 ~ I-29 can by the method of Synthesis Example 1 can be prepared, wherein the starting material is changed.

The compounds I-30 ~ I-39 can according to the procedure of Synthesis Example 2 in which the starting materials are changed.

Compounds I-1 ~ 1-39 are general in the art known.

As examples of the polyalkylene oxide derivatives used according to the invention are the addition polymerization products between alkylene oxides such as ethylene oxide or propylene oxide and a compound such as water, an aliphatic alcohol, an aromatic alcohol, glycols, fatty acids, organic Amines and a dehydrated compound of a hexitol derivative, condensates of a polyalkylene oxide with a Compound of the type described above, or block copolymers of various alkylene oxides such as ethylene oxide-propylene oxide Block copolymers as described in US Pat. No. 3,516,380 and the like indicated. Further Examples of such materials are for example in U.S. Patents 2,400,532, 3,294,537 and 3,294,540 to French Patent documents 1,491,805 and 1,596,673, in the Japanese

309827/0882

niches Auslegeschrift 23466/65 etc. inscribed2 2638 O 8

The polyalkylene oxide derivatives used according to the invention are those with a molecular weight of 500 to 12,000, preferably 800 to 6000. Particular examples of these are the following:

(a) HIGH ₂ CH ₂ C (CH ₂ CH ₂ O) ₃₀ - ^ - C ₉ H ₁₉

(b) HOCH ₂ CH ₂ 0 (CH ₂ CH ₂ 0) ₄₀ CO (CH ₂ ) ₂ CH = CH-C ₈ H ₁₇

(c) H0 (CH ₂ CH ₂ 0) _a (CHCH ₂ 0) _b (CH ₂ CH ₂ 0) _c H

where b is an integer from 14-55 and a + c is an integer from 4-210. Such materials are commercially available under the trade names "Pluronic L-44, L-6I, L-62, L-64, L-68, L-81, P-65, P-75, F-88", etc. ( Wyandotte Chemical Co.). In Pluronic L-68, for example, the molecular weight is 8750, b = 32 and a + c = 159; in Pluronic P-75 the molecular weight is 4100, b = 37 and a + c = 51; and in Pluronic F-88 the molecular weight is 11,250, b = 4i and a + c = 204. (d) HOCH ₂ CH ₂ O (CH ₂ Ch ₂ O) ₅₀ CH ₂ CH ₂ OH

CH ₂

C ₁₂ H ₂₅ COO-CH CH-O- (CH ₂ CH ₂ O) _1n PI CH

) - (CH ₂ CH ₂ O) _n H where. £ + iii + n = about 20 and. U) H0CH ₂ CH ₂ 0 (CH ₂ CH ₂ 0) ₄₉ - ^) - C ₄ H ₉ (t).

The compounds of the above general formula (I) used according to the invention are represented by the Presence of a functional thioketone group. According to the invention, it is important that compound (I) a has functional thioketone group and that the substituent R is a substituent other than hydrogen atom. Such a one Compound provides effective results in combination with a polyalkylene oxide derivative. As in these compounds

309827/0882

R does not represent a hydrogen atom, the compounds can not form a tautomeric isomer with a mercapto group, and there is no decrease in sensitivity when these compounds are used. In contrast, these compounds provide a supersensitizing effect with most commonly used simple merocyanine dyes, dimethine merocyanine dyes and carbocyanine dyes, and therefore they can increase sensitivity without increasing fogging.

309827/0882

The sirber halide photographic emulsions according to the invention can be spectrally sensitized are determined, for example, by using one or more sensitizing dyes of the following general formula (II) or (III):

General formula II _v

/ ¹ ^

CC = CH-L) _n = C

^E 4

wherein Z ^ the atoms required to form a tetrazole nucleus, pyrrolidine nucleus, pyridine nucleus, thiazole nucleus, thiazoline nucleus, selenazole nucleus, selenazoline nucleus, oxazole nucleus, oxazoline nucleus, indolenine nucleus or imidazole nucleus, L is a methine chain, for example an optionally substituted methine group (C, ₁ -C ^ - ^ substituted methine group or a phenyl substituted methine group, Yy, an oxygen atom, sulfur atom or = NR, -

(in which R ^ - an alkyl group with 1-6 carbon atoms, e.g. methyl, ethyl, propyl, cyanoethyl, allyl, carboxyethyl, dimethylaminoethyl, benzyl group or the like, an aryl group, for example phenyl or p -Sulfonylgruppe), η the number 0 or 1, R ^ and R _n - an alkyl group (e.g. methyl, ethyl, carboxyethyl, carboxybutyl, sulfoethyl, sulfopropyl, allyl, morpholinoethyl, acetoxypropyl, benzyl group or the like), an aryl group OjZ.B. Denote phenyl, tolyl, pyridyl group or similar groups,

General formula III

309827/0882

where A is a hydrogen atom, a lower alkyl group with not more than 3 carbon atoms, e.g. methyl, ethyl, propyl group or the like, Z ₂ and Z, which form an aromatic ring of the benzene series such as 5-phenylbenzoxazole'-, 5-chlorobenzoxazole -, 5 -Met hoxy carbonyl benzoxazole, 5-Acetoxybenzoxazol-, 5-Chlorbenzothiazol-, _5-chloro-6-T 5-Methylbenzothiazol- Methoxybenzothiazol-, benzoselenazoles 5 ~ Methylbenzosel & nazol-, 5,6-dichlorobenzimidazole _T, 5-chloro -6-methylsulfonylbenzimidazole ring

atoms required or those needed to form an aromatic

Alles

Ring of the series of naphtha ^ .B. Naphtothiazole, naphtoselenazole or naphtoimidazole ring required atoms represent, the information benzene and naphthalene series so / ohl include substituted and unsubstituted benzene and naphthalene, for example, the substituent is an alkyl group, usually a C ^ -CL ,, preferably Cy, -C ^ - alkyl group, a halogen atom or a phenyl group, Yp and Y ₂ an oxygen atom, sulfur atom, selenium atom or -NR ^ C where Rr _{7 is} a (C ^ -C ^ -) - alkyl group, preferably a Cy. - C ^ - alkyl group, such as methyl, ethyl, allyl, acetoxyethyl, CyanoäthyIgruppe or the like means), Rj and R, - an alkyl group with not more than 6 carbon atoms, for example methyl, ethyl, propenyl -, Hydroxyäthyl-, Amidoäthyl-, Carboxypro] jrl-, SuIfoäthyl- * 4-sulfobutyl-, 2- ^ 2- (3-sulfopropoxy) ethoxy7 ethyl, propylene sulfate group or a group as described in "Zeitschrift für Wissenschaftliche Photographic," Volume 63, pages 149-158, 1969, contribution by EJPoppe, are given, X ~ an anion as it is used in the synthesis of cyanine dyes, for example a bromide, Τοαιαίοη, p-Toluoioulf onatanion, Perchloratanion or the like, ρ the number 1 or 2, and when an inner salt is formed, ρ denotes the number 1.

309827/0882

Compounds of general formula II are described, for example, in French patent specification 1,596,673. Specific examples are given below.

Compounds of the general formula III can according to those described in U.S. Patents 2,503,776 and 3,177,210, the British patent 7 ^ 2 112 and the German Patents 1,072,765 and 1,163,671 specified procedures can be prepared.

The added amounts of the compounds of the general formulas II or III are the same as those for the compound of the general formula I.

= CH

= CH -

309827/0882

H,

H ₂ CH ₂ C

CH

'C

N-C

-CH - CH =

-Ν

= CH - CH =

NC ₂ H ₅

H ₂ C

Ή.

-N-CH.

CH - CH =;

vS "

C ₂ H ₅

309827/0882

H ₂ O

ΓΗ

C ₂ H ₅

2 ^Η 5

-.0

^H 3 °

V- V / .1Jl-Wil-i

C = CH-CH = <

C ₂ H ₅

NC ₂ H ₅

309827/0862

C ₂ H ₅

H,

x>

CH ₂ CH ₂ OH CH ₂ CH = CH ₂

= S

CH:

CH ₂ CH = CH ₂

CH ₂ CH ₂ COOH

309827/0882

H ₂ C

₌ cH - CH = r ""

N CH-

CH ₃

= CH - CH

NC ₂ H ₅

\ jH ₂ CH = CH ₂

CH-

O-

CH ₂ CII ₂ OH 0 '

309827/0882

CH-

S J>

> = CH -

■ Η '
CH.

Specific examples of compounds of general formula III include the following compounds:

= CH-C = CH

(CH ₂₎ 33O3HH

309827/0882

(CH ₂ J ₃ SO ₃ HN (C ₂ H ₅ )

CH

Se

CH

■ N

CH.

(CHg) ₃ SO ₃ Na

CH ₂ CH = CH ₂

H _n CH = CH,

C.

. I.

(CH ₂ CH ₂ O) ₂ (CH ₂ ) ₃ S0 ψ (CH ₂ CH ₂ O)

O / T ^

309827/0882

C ₂ H ₅

-CH = C-CH =

CH ₂ CH ₂ COO

CH ₂ CH ₂ COOH

(CH ₂ ) ₄ SO (CH ₂ I ₄ SO ₃ Na

309827/0882

OOCH.

(CHg) ₃ SO ₃ HN (C ₂ H ₅ )

Se

CH

V-CH = C-CH =

C ₂ H ₅

O. C ₂ H ₅ = CH-C = CH

C ₂ H ₅ N

OCH-

CP.

(CH ₂ I ₃ SO ₃ Na

309827/0882

The silver halide emulsion used in the invention can be a silver chloride, silver bromide, silver iodide emulsion, or a mixture thereof. In particular silver chlorobromoiodide emulsions ^ which contain silver chlorobromide and less than 2 mol% iodide ions, preferred. In addition, silver halide emulsions containing grains are their most common size is less than 0.8 microns and that is at least 50 mole percent Containing chlorine ions as grain-forming components are suitable. Usually the most common size is in the range of 0.04 to 0.8 microns, preferably 0.2 to 0.8 microns.

Preferred emulsions for use in accordance with the invention have a silver halide grain size of 0.1 to 1 micron and contain 30 to IpO g per 1 mole Silver halide from a hydrophilic colloid material. The particularly preferred hydrophilic colloid material is gelatin. However, they only represent preferred embodiments and are not intended to be limiting of the invention.

In the emulsion, one or more hydrophilic colloidal materials are used as dispersant and accurate material which reaches the application is not excessively Heist kritisch.Das, it can ^ materials such as gelatin, gelatin derivatives, such as
Cellulose derivatives such as hydroxyethyl cellulose or carboxymethyl cellulose, soluble starches such as dextrin or starch made alkaline, hydrophilic polymers with high molecular weight such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide or polystyrene sulfonic acid and similar materials can be used.

The emulsion can be chemically sensitized by any known technique, e.g. by sulfur

or malonylated phthaloylated components,

309827/0882

sensitization, reduction sensitization, sensitization with precious metal ions, e.g. a gold compound, a platinum compound or the like, or a combination of these operations. aside from that other metal ions than silver ions, e.g. Group VIII metal ions and Group II metal ions are used to sharpen the contrast of the gradation, to stabilize the emulsion, the formation of fog to control and to give the emulsion an oversensitization.

The emulsion can contain an additive of a stabilizer (e.g. 4-hydroxy-1,3, j5a-7-tetrazaindene derivative), a Antifoggant, a hardening agent, a surface-active agent, a hydrophilic synthetic polymer, contain a latex polymer and a dye to prevent radiation, all additives thereof usually "in the manufacture of photosensitive Materials are used.

The compound used according to the invention is generally used Formula I is preferably used in an amount of about ΊΟ "" to about "10" * moles per 1 mole of silver halide are used. That Polyalkylene oxide derivative is preferably added in an amount of about 0.01 to 1 g per 1 mole of silver halide. Optimal results are obtained when used within these amounts.

If the connection is? adjacent layer> e.g. a top layer, a back layer, an antihalation layer, an intermediate layer or a silver halide layer when incorporated, the amount of the compound becomes greater than that contained in the silver halide emulsion layer Related to silver halide into which the compound from the adjacent layer diffuses.

309827/0882

The compound of general formula I and the polyalkylene oxide derivatives can be added by they are in water, in alcohols which are miscible with water (e.g. methanol, ethanol, methylcellulose solvent or the like), or ketones (e.g. acetone or the like.), and then either directly added to the emulsion or to an adjacent layer Formation of a multi-density structure admits *

An emulsion completed according to the invention is applied to a suitable support, e.g. a glass plate, Cellulose acetate film, cellulose acetate butyrate film, polyester film or a similar plastic film or the like. Applied for use. Although paper is used it is not used in normal practice.

An antihalation layer or a filter layer can be on or under the emulsion layer according to of the invention can be provided.

The photosensitive material obtained according to the invention Silver halide material can be used in irgeicbiner known ways are treated and processed. For example, an infectious developer is used during development. Such infectious developers basically include dihydroxybenzene (developing agent) alkali, a minor one Amount of sulfite and a sulfite ion buffer.

The developing agent, namely dihydroxybenzene, can can be selected from those known in the art of photography. Specific examples include Hydroquinone, chlorohydroquinone, bromohydroquinone, "isopropylhydroquinone, Toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone or the like hydroquinone is particularly preferred. This developer agent

309827/0882

can be used individually or in the form of combinations thereof.

A sulfite ion buffer is used in an amount sufficient to effectively keep the sulfite concentration in the developer low. Examples of such materials are aldehyde-alkali hydrogen sulfide - plant products _; 2 B. Formalin-sodium hydrogen sulfite adduct, ketone-alkali metal hydrogen sulfite adducts - for example acetone-sodium hydrogen sulfite adduct, carbony-bisulfite condensation products, for example sodium bis (2-hydroxyethyl) aminomethanesulfonate or the like.

The developing agent or agents become used in amounts as are customary in the previously known infectious developers, e.g. in an amount from about 5 to 50 g developer agent or from developer » average a 1 developer each, preferably 10 to 30 g each Liters of developer. The same is generally true of the sulfite ion buffer, and such materials are common used in an amount of 13 to about 1JO, preferably 30 to 60 g per liter of developer.

The alkali material is added so as to make the developer alkaline, i.e., to make it preferable to give a pH of above 9. The kind of alkali is not limited and any s of commonly used in photographic technology Means can be used for this purpose ^ e.g. Carbonates such as calcium carbonate, sodium carbonate or calcium carbonate or the like. Borsgc and see, - or tertiary phosphates such as disodium phosphate, trisodium phosphate or the like.

309827/0882

The developer can also contain various additives known to those skilled in the art, e.g. an organic antifoggant such as benzotriazole, i-phenyl-5-mercaptotetrazole or the like, polyalkylene oxides, Amine compounds, organic solvents, e.g. triethylene glycol, dimethylformamide, methanol, ethylene glycol monoalkyl ether or the like.

When using the photosensitive material according to the invention, a gradation of high contrast can be achieved with a good curved tail piece or a good lower one

Cecil ")

Part of the blackening curve.without the need for a comparatively long development like this "in the treatment of conventional light-sensitive silver halide materials, in which a polyalkylene oxide derivative is used, is required, can be obtained. It can also have the effect that the quality of each Points is uniform.

The invention is explained in more detail below with the aid of examples.

example 1

A chemically ripened silver chlorobromoiodide gelatin emulsion (14g gelatin / 1 mol silver halide) was prepared in the usual way, that is, by adding aqueous solutions of silver nitrate and potassium halide to an aqueous solution of gelatin, physically ripening the same and then adding a gold salt and sodium thiosulfate to the mix. The bromide ion content and the iodide ion content in the emulsion were 17 mol% and 0.2 mol%, respectively. The amount of silver was ¹ per 1 kg of the emulsion

309827/0882

about 1.3 Hol and the most common size of the silver halide grains was 0.6 microns. 700 g portions of the resulting
Emulsions were weighed into 20 vessels. Each emulsion was prepared according to the procedure given in Table I below. The production was carried out as follows:
Each vessel was ^{heated to 45 °} C. with stirring;

(1) the spectral sensitizing dye was added;

(2) a compound from the group of compounds of the general formula I was added and

(3) the polyalkylene oxide derivative was added.

Table I. Additional amount
ml ■
(Mol-Κοήζ.je
1 ml) * Connection of the general
Formula I. additive
quantity ml
** Polyalkyleneoxy <
derivative aisatz
Length sample
No. Awareness
dye Connect
manure Connect
manure 20th Connect
manure 50 _4 - O), Il 1
2 - Il 20th O) Il 3 (B) Il 1-2 40 O) 20th 4th (B) dd 1-2 20th O) It 5 (B) ti 1-25 40 O) Il 6th (B) ti O) Il 7th (B) (2x1O ~ ⁵ ) - (2) 11 8th - Il mmm 20th (2) Il 9 (C) 1-5 (2) 10 (C)

309827/0882

11 (Cj 12th '· V V' / 13th (C) 14th - 15th (A) 16 : (A) 17th (A) 18th (A) 19th (A) 20th

« 1-22

Il -Il

(5 χ 10 ^J )

ι i_29

1-2 1-2

40 2263808
(2) Il 20th (2) ti 40 (2) Il (3) 12th (3) It 20th (3) Il 40 (3) left (D 20th 40 (D ι! 40 (D Il

In the table given above, "mean:

(A): 1-ethyl-3-ethyl-5- (3-sulfopropyl-2-benzoxazoliniden) Ethylidene-2-Thiohyda ^ .toin,

(B): Anhydro-11-ethyl-3,3'-bis (sulfopropyl) -naphtho- / _1,2-dJ thiacarbpcyanine hydroxide.

(C): 9-methyl-3.3 ^l -bis (. Sulfobutyl) -selenacarbocyanine hydroxide, (1): polyethylene oxide derivative with a content of about 50 ethylene oxide chains per oleylphenoxy group; Molecular weight about 2600,

(2): polyethylene oxide derivative with a content of about 30 Ethylene oxide chains per oleyl alcohol group; Molecular weight about 1500,

(3): polyalkylene oxide derivative of a block copolymer with a molecular weight of about 2000 and a content of polypropylene oxide chains and polyethylene oxide chains; the numerical ratio from PropylenoxydgMppen to Äthylenoxydgtnppen in that Molecule is about 30: 8,

309827/0882

(4): ethylene oxide derivative containing about 60 ethylene oxide chains ge oleylphenoxy group; Molecular weight around 3500.

* Molar concentration and amount of methanol solution added Sensitizing dyes are indicated.

** Methanol solution with a molar concentration of

-3
5 x 10 ^ 1 il each was used. *** 0.5% by weight of an aqueous solution was used.

10 ecm of a 1% aqueous solution of liatrium dodecylbenzenesulfonate and 10 ecm of a 2% strength aqueous solution of the sodium salt of 6-hydroxy-2,4-dichloro-S-triazine were each of the emulsions thus obtained as

TO"·

Apply coating aid and the emulsion obtained was then applied to a cellulose triacetate film to a dry thickness of about 4 / U, followed by drying became.

The coated ITiIm was cut into strips and the resulting strips were measured with a wedge using a light source of 2854 ⁰ K by means ^of: exposing a Serätometers during a second (250 lux) The exposed strips were developed using the developer indicated below, the Usually used in the development of lithographic photosensitive materials, developed at 20 ° C for 1.5, 3 minutes or 4 minutes and then fixed.

Composition of the developer:

Water (about 30 ⁰ C) 500 ecm

Anhydrous sodium sulfite 30 S Paraformaldehyde 7.5g

309827/0882

Sodium bisulfite 2, 2 G Boric acid 7, 5 ε Hydroquinone 22 5 G Potassium bromide "1, 6th G Water rest on L

The density of the strips so treated was measured; to get the characteristic curves of the strips. The results obtained are shown in Table II below.

309827/0882

TaToIe

CaJ O CD CX)

O OD OO

"Relative Recommend it 4min. Contrast (J) 3min. ·. 4min. j point quality C. .'4min. Note:
kung I. ^^^ - Sn ^ winding s -
Specimen eoier ^ 1.5min. 3min. 15.5 1.5min. 5 ¹ ^ 5 1.5min. C. D. .-22638C . 1 5.6 12.3 3.1 6th > 13 * C. B. D. 1) Fi ^ -1IMl "
OO CvJ - 1.8 6.3 - 8th 12th D. ■ A σ 2) Fi
Curve 3 - 5.2 15.1 ~ - - • 9 ^V 13 D. A. B. 4th 1.4 9.1 27.6 8th > 13 8th C. A. ? ■ VJl 2.4 13.8 31.6 10 10 10 B. C. A. east
CO 6 ' 2.6 19.0 36.4 10 > 13 6th B * D. B. 7th 6.0 18.6 4.0. 11 10 > 13 " B. B. B. 8th - 1.8 3.1 - 4th >! 3 D. B. D. 9 · ^ -. ".. . 1.5 17.4 - > 13 > 13 D ' B. 10 1.5 10.0 28.1
10
28.2 7th 8th
7th
6th 8th
7th D. • 'Β
. B.
B. 11 ·
'12. '*
13th 2.4
1.6 14.8
3.8
.12.6 ' 12th B.
D.
D.

HH Hcvl inH sfOJ ^ uu-

ώ _C) 'ώ <· £ · Μ-ϊ »S» ι? 9? R 7 R Π3

⁴ TO ^ ro "" in * "VO C-

pq W pq < O PP FQ

p fq <; <J fQ <ij "FQ

C- O rO rO C- να H H H H A. ro VD c- ro in ro - cn H ro ro ro H C- r4 H H / N ro ^ / \ ro ¹ co H rO ro ro H H I. H H H -. ■ ι ' ^N O- c- in VD in O in cn CO CvI in CvI O Sf co H VD VD sf- H O irv ro H VD O in co cn ■ ·
H ro CvI O O sf- ro ro H CT> in Sf- • in O cn O co H (M ro I. CvI CO c-

in vo Γ ΟΟ cn O H H H H CvI

309827/0882

In Table II given above, the relative sensitivity is expressed in terms of the relative value of the reciprocal amount of exposure corresponding to the point in the characteristic curve ^ for polygons the optical Density is 0.5. The contrast is in terms of mean slope (f) on the linear part indicated on the characteristic curve. "-" means that the value is too was low to be measured with accuracy, while "> 13" means that the value was too large to be can be measured with accuracy, namely at least above 13

The dot quality rating was determined by placing a contact screen (133 lines / 2.54-cm (1 inch)) tightly on a sample and exposing the sample to light and developing it in the same manner as described above _x and the dot image thus obtained with an optical micro

was observed. The samples were wuiden. classified into M grades with an even distance from one another, namely A (best) B, C and D (worst ^ unsuitable for practical purposes) in the order of magnitude of the sharpness of their point edges.

The results of this' assessment process fall approximately on the order of the magnitude of the Edge gradients obtained by measuring the micron density of the point image using a micron densitometer will.

In Figs. 2- M-, there are shown curves illustrating the relationship between the distance and the optical density with respect to the edge portions, the relationship being based on an average of 6 points.

309827/0882

These were determined by measuring the density of a point image with the following mean density of a microndensitometer with an aperture of 2 / U times 1O, starting with the low density side

obtain. Medium density Point quality 0.40 D. Pig. 2 curve 0.38 C. Fig. 3 curve 32 0.40 B. Pig. 3 curve 31 0.37 B. Fig. 4 Curve 41 0.37 A. Fig. 4 curve 42

The curve 51 in FIG. 5 shows the range of individual curves _? which were used to obtain curve 41 in FIG. 4 and curve 52 in FIG. 5 shows the area with the curve in FIG. 4. It can be seen that the quality of the individual points was made uniform by the presence of the compound of the general formula I according to the invention.

Examining the results detailed in Table II, it can be seen that the photosensitive Silver halide material containing neither the compound of the general formula (I) nor the sensitizing dyes of the general formula II or III, i.e. that it contained only one polyalkylene oxide derivative, the tendency occurred that the longer the development time, the higher both the relative sensitivity and the contrast and the more the point quality was improved. (Compare samples 2,8, and 14)

309827/0882

In the case of adding the sensitizing dye it of the general formula II or III _? however, without the addition of the compound of general formula I, the sensitivity increased with increasing development time. However, in this case, there was no great change in contrast (see Sample 3) and an adverse effect occurred in some cases (see Sample 9), although there were cases where both the sensitivity and contrast were good (see Sample 15) and 18). however, the dot quality was not improved in proportion to the sensitivity and the contrast.

It can be seen, however, that by using a system according to the invention an excellent high contrast photosensitive material having a higher sensitivity than that of any of the common materials that have a good point quality delivered », could be obtained (compare, for example, sample or 20 according to the invention with sample 18 of a comparative sample).

309827/0882

A chemically ripened silver chlorobromide gelatin emulsion (74 g gelatin / 1 mol silver halide) was prepared in the usual manner as indicated in Example 1. The bromide ion content in the emulsion was 30 mol % and the amount of silver per 1 kg of the emulsion was about 1.1 mol.

Samples of the light-sensitive material prepared according to the procedure set forth in Example 1 under the conditions indicated in Table III and subjected to a sensitometry, as indicated in example 1 _V,. The results obtained are shown in Table III.

The information in Table III has the same meaning as in Tables I and II above.

309827/0882

No.- link
the general
my For
mel (I) Quantity (ecm)
(Molar concentration
tration) 10 " ³ ) T
Polyalkyls
oxydderiva abelle III Quantity (ecm)
(Weight
percent) - Relative
sensitivity 3 ^f 4 » 2- races (Y) Point-
Quali '3 ^T 21 - 10 " ³ ) n-
t l ^! 30 " 12.5 16.2 3 ^f '• 4 « l'3O " D. 22nd - 10 ~ ³ ) 4th (ofsfc) 6.0 2.0 3.1 5 4th D. . B. 23 1-19 100
(2 χ 10 " ³ ) 4th 11 1.4 12.6 24.0 11 11 D. A, 24 1-2 · 50
(2 χ 10 " ³ ) 4th 11 2.4 8.0 15.9 > 13 7th B. I. 25th It 100
• (2 χ 10 " ³ ) 4th ti. 1.9 9.5 16.0 8th B. A. I. 26th ti 150
(2 x 10 " ³ ) 4th 11 2.3 9.3 17.8 as 8th B. A. 27 1-39 50
(2 χ 10 " ³ ) 4 ' • 11 2.8 14.0 1.58 as _r , A. B. • 309 28 It 100
(2 χ 10- ³⁾ 4th 11 3.6 12.1 ■ 18.8 11 6th A. B. OO
rsj «
-a 29 ti 150
(2 χ 4th It 2.7 11.2 16.0 8th 6th A. B. co
OO 30th 1-18 100
(2 χ Λ Il 3.0 2.0 6.8 7th 6th A · B. 31 ti 150
(2 χ 4 " ti 1.1 2.4 7.1 ω M3 B. A. 1.6 & 3 W. B. COOQ
Kent 1'30 6th 6th > 13 10 10 > 13 > 13 > 13 > 13 6th 7.1

~ 46 -

It can be seen from the results of Table III that, according to the invention, the dots are of good quality and that high sensitivity can be obtained using a short development.

Preferred embodiments according to the invention are listed below:

(T) According to the invention, a silver halide emulsion formed with a sensitizing dye represented by the general formulas (II) or (III) is spectrally sensitized is used.

(2) According to the invention, an emulsion comprising silver halide grains having a common grain size of contains less than 0.8 microns and at least 50 mole percent silver chloride.

309827/0882

Claims (11)

Claims 1. A photosensitive silver halide material characterized in that it contains at least one compound of the following general formula (I) .and at least one polyalkylene oxide derivative in a silver halide emulsion layer or contains a layer adjacent to this, where in the formula given above Q represents the atoms required to form a heterocyclic ring and R represents an alkyl, aryl or hetero group, 2. silver halide material according to claim 1, characterized in that that the polyalkylene oxide derivative has a molecular weight of 500 to 12,000. 3. silver halide material according to claim 1, characterized in, that the silver halide has a most common grain size of 0.2 to 0.8 microns. 4. silver halide material according to claim 1, characterized in that that the silver halide emulsion layer contains a hydrophilic colloid. 5. silver halide material according to claim 1, characterized in that that the compound of the general formula (I) -6 - "5 in an amount of from about 10 to about 10 moles and the polyalkylene oxide derivative in an amount of about 0.01 to about 1 g per one mole of silver halide in the silver halide emulsion layer available. 6. Silver halide material according to claim 1, characterized in that Q in the general formula (i) is used to form a hydrocyclic ring from the group of benzothiazoline-2-thione, imidazoline-2-thione, selenazolidine-2-thione, 1,3 , 4-thiadiazolin-2-thione, 1,3,4-selenadiazolin-2-thione, 4-selenazolin-2-thione, 1,2-dihydropyridine-2-thione, benzoxazo- 309827/088? lin-2-thione, benzimidazoline-2-thione, benzoselenazoline-2- thione and 1,2-dihydroquinoline-2-thione ring represents the required atoms . 7. silver halide material according to claim 6, characterized in that R in the general formula (I) is a Represents an alkyl group having 1-13 carbon atoms, an aryl group or a heterocyclic group. 8. silver halide material according to claim 7, characterized in that R is a methyl, ethyl, propyl, hexyl, Decyl, hydroxyethyl, benzyl or a morpholinoethyl group represents. 9. silver halide material according to claim 7, characterized in that R is a phenyl, 2-methylphenyl, Represents 4-methoxyphenyl or a 4-chlorophenyl group. 10. silver halide material according to claim 7, characterized in that R is a 2-pyridyl or dipyridyl group represents. 11. silver halide material according to claim 1, characterized in that the polyalkylene oxide derivative from the group of (a) HIGH ₉ CH ₉ C (CH ₀ CH ₉ OU _n C _b H_ _Q (b) HOCH ₉ CH ₉ O (CH ₉ CH ₉ O), _n C0 (CH ₉ ) _CH = r CH-C ₀ H ₁ " d d dd 4w dd ο J. / Cc •) HO (CH ₉ CH 0) _q (CHCH ₉ O), (CH ₉ CH ₉ O) H C-C-AX C. U dd ^ CH ₃ where b is an integer from 14-55 and a + c is an integer from 4-210, 309827/0882 ~ 49 - (d) (e) C-, yes _{0 (} -coo-CH v / orin 2 + in + η = about 20 and (f) HOCH ₂ CII ₂ O (CH HO- (CH ₀ CH ₀ O) H d d ΙΟ. is chosen. ° 4 ^H 9 ^(t) 309827/0882