DD157147A3 - PROCESS FOR INTRODUCING HYDROPHOBIC PHOTOGRAPHIC ADDITIVES - Google Patents

Abstract

The invention relates to a process for introducing water-insoluble photographic additives, in particular color couplers, into aqueous media using high-boiling organic solvents. The aim of the invention is the incorporation of hydrophobic photographic additives, in particular color couplers, in gelatin or other hydrophilic binders. The invention has for its object to provide a new, high-boiling solvent for the dispersion of hydrophobic photographic additives. According to the invention, this is achieved by using phosphorus acid triamides of the general formula and / or other phosphoric acid esters as the high-boiling solvent. The advantage of the process of the invention for introducing hydrophobic photographic additives is a reduced tendency of the additives to crystallize. This results in stable dispersions, which are characterized by good compatibility of the new high-boiling solvents with gelatin and by no negative influence on the photographic properties.

Description

-Ά-

Method for introducing hydrophobic photographic additives.

The invention relates to a process · for the introduction of water-insoluble photographic additives in particular _s of color couplers, in aqueous Medien'unter application of high-boiling organic solvents ^

In the manufacture of photographic materials, a number of hydrophobic excipients, particularly color couplers, mask dyes must _s stabilizers are introduced among others in the hydrophilic materials "is known, this happens in such a way that the hydrophobic substances in an organic, heavy-volatile solvent, in the literature often as Crystalloid, and this solution is dispersed in an aqueous medium. Often, low-boiling auxiliary solvents,

such as ethyl acetate, chloroform ,. Methylene chloride u- a. used with, which are then removed again after the D.ispergierung »is obtained a dispergate containing the color couplers in the form of extremely fine droplets in the hydrophilic binders of the photographic layer as the hydrophilic binder is preferably gelatin in question, but can also be used other polymers colloidal binders are used "numerous high-boiling organic solvents for the 'dispersion of photographic additives" known _e Thus 629,842 benzoic to DE-OS 2 129 684 formamides, according to US 2 ~ 5335H Mbutyllaurylamid and after D3-6S-2 used "

Also known is the use of phthalic acid esters, tricresyl phosphate or according to DE-OS «-2 042581 of phosphoric acid esters which contain not only aryl groups but also aliphatic groups, such as, for example, di (n-hexyl) phenyl phosphate or tris (2-ethyl) hexyl) phosphate. Commonly used solvents for the delivery process have a number of disadvantages such as "insufficient solvency for the photographic excipients." For example, color photographic materials contain color couplers dispersed as developing components prior to development The quality of the color material thus depends, inter alia, on the dissolving power of the solvent used during dispersion, both with respect to the color coupler and with respect to the resulting image dye, with decreasing solvent power one must use more solvent *. Incompatibilities with the hydrophilic binder are observed in many cases and it comes to Ausschwitzerscheinungen * This leads to lower dispersion stability and difficulties in the Further processing • Insufficient solvency is also the

Λ i Q / 0 £ f ta 2 cn

Reason for insufficient surface concentration of the color coupler and thus too low opacity of the resulting color image »

goal of

Object of the invention ^ the development of a method for introducing the hydrophobic photographic additives, particularly color couplers, .in gelatin or other hydrophilic binder which the disadvantages of known methods, such as "B _e zu_geringe Disperoionsstabilität, recrystallization of the hydrophobic additives and demixing * avoids phenomena in the photographic layer.

The invention is based on the object of specifying a new, high-boiling solvent for the dispersion of hydropionic photographic additives.

DESCRIPTION OF THE NATURE OF THE INVENTION According to the invention, this is achieved by using phosphoric acid triamides of the general formula I as the high-boiling solvent. _ · - -

/ ¹

SP-5v ^K 5 N ^K 2

^R 4 ^R 3 · · ..

and / or phosphoric monoester diamides of the general formula

/ NP-OR ₇

R ₂ R ₁

and / or phosphoric acid diester monoamides. the general formula? ,

Rp 0

/ NP- OR ₇

~ 4

used, where R., IL), R * _,? R ^ * Rj-? R independently of one another are hydrogen atoms, alkyl, cyclohexyl, alkenyl, cyclic radicals, phenyl, benzyl or substituted aryl radicals, R "and Rq alkyl, cyclohexyl, alkenyl, alkoxyalkyl, carboxyalkyl, aryloxyalkyl, chlalkylalkyl , Phenyl, benzyl or substituted aryl radicals and the number of carbon atoms of the substituents R ₁ , Rp,. R ", R / Rn together form 10 to 96 and the number of carbon atoms of the substituents R ₇ and Rg is 2 to 40.

Optionally and independently of one another, each of two substituents R ₁ to Rg which are the same as nitrogen, together with this nitrogen, may form a cyclic radical, where this radical is ethyleneimide, piperidine, partially or pherhydrated quinoline, isoquinoline or morpholine.

If the substituents R ^ to Rg represent substituted aryl radicals, these are understood as meaning benzoic acid esters having 1 to 5 carbon atoms in the ester radical and in the substituents R and Rg the alkoxyalkyl radicals represent groups having 1 to 4 carbon atoms in the alkoxyreet, the carbocyalkyl radicals groups having 1 to 5 Carbon atoms in the carboxy radical, the aryloxyalkyl radicals are groups with phenyl or ghorphenyloxy groups in the aryloxy radical and the substituted aryl radicals, alkylphenyl having 1 to 15 carbon atoms in the alkyl radical or chlorophenyl. The compounds according to the invention are prepared by known processes as described in Liebigs Anna. 326 (1909) or in Houben-Weyl Handbook of Organic Chemistry Bd " TL1 / 2. Examples of the compounds according to the invention are: phosphoric acid trie." [dipropylacid] phosphoric acid tris [di-n "butylamia] phosphoric acid trisulfonic acid. [propyläraid] phosphoric acid diphenyl ester diethylamide phosphorus acid monophenyl-styrene »-dipiper id id phosphoric acid» diethyl ester dodecylamide

Phosphoric acid ethyl ester dipiperidid. Phosphoric acid diphenyl ester "" tetrahyaiOch.inolid phosphoric acid "adiäthylester-in-amino-betzoesäureetbyl esterJ ^ affiid

Phosphoric acid »diphenyl ester« Ethyl alyid Phosphoric acid »Diphenylester-β-morpholide Phosphoric acid« n »Butylene ter.« To ~ Cdi »n« »butylamidejf Phosphoric acid *> n = octylester-bis-diethylamidej

Phosphoric acid octractadecyl ester-bls-dimethylamide] phosphoric acid «diethylaraid-

Phosplioreäure ^ monopentachlorphenyl & art ^ up ^ pi ^ n ^ butyl ·

Phosphoric acid <= tnono (p »dodeeylphenyl) est *

Ph.osphorsäure "up" (p »nonylphenylester)» diethylamide

Depending on the structure of the color couplers or other hydrophobic additives to be dispersed, the amount of phosphoric triamide is from 25 to 200 % ₉ based on the amount of hydrophobic photographic additives. It is also possible and particularly advantageous in certain applications mixtures of different phosphoric acid triacd.de ₉ Phosphoric acid monoester diamides; or phosphoric acid "diesters" may be used in the presence of other known high-boiling solvents, such as phosphoric acid star or tricresyl phosphate. "

Likewise, low-Hilfslösungsaittel can be with used which are removed by distillation before Bsguß or by watering "> Examples Items since Xthylasetat, propyl acetate, methylene chloride, chloroform or methylene" ethyl ketone "'. Also, polymers or oligomers can the dispersing solution are added to _e

• 21 8 4 O "4 - 6 - .. -

The dispersion takes place in a known manner with the addition of surface-active substances which can be used both in the organic or aqueous phase or in both phases. Suitable anionic surfactants, nonionic surfactants or mixtures thereof are known for this purpose. Examples are; Alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl ethers, and sulfate esters thereof, such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, w4-4-thioxy-thyl, etc., such as polyoxyethylene lauryl ether, Sodium polyoxyethylene lauryl ether sulfate, polyoxyethylene alkylaryl ethers and sulfate esters thereof such as polyoxyethylene nonylphenyl ether or sodium polyoxyethylene nonylphenyl ether sulfate, polyoxyethylene ^1- alkyl and sulfate esters thereof such as polyoxyethylene stearic acid ester, polyoxyethylene palmitic acid ester or sodium polyoxyethylene stearic acid ester sulfate *

As hydrophiles.schichtbildendes colloid preference "is as gelatin used," but may also include other known hydrophilic polymers such as, _e B _4, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, cellulose derivatives, or mixtures thereof are used with gelatin · The advantage of the inventive method for introducing of hydrophobic photographic additives consists in a reduced crystallization tendency of the additives, Ea arise stable dispersions, which are characterized by good compatibility of the new high-boiling solvents with gelatin and by no adverse effect on the photographic properties *.

10.g photographic yellow coupler of the formula:

Cl

* NH ~ CO - CH ₂ ~ CO - @ - NH - CO - C,

are dissolved in a mixture of 30 ml ethyl acetate and 8 ml of phosphoric acid iris "dipropylamide 40 ⁰ C * the solution with eineoi high speed Schnei! stirrer at 5O ⁰ G in a mixture of 90 ml 10 # gelatin solution and 20 ml of 4% Uatriumdoaecylsulfatlösung emulgierto a homogeneous the dispersed material from which then at 6O ⁰ C, the ethyl acetate is removed by distillation under reduced pressure again "after pouring the dispersed on a transparent substrate is obtained by drying a clear layer

10 g photographic yellow coupler of the formula! OCH ₃

M - CO - CH ₂ «CO» (g ^ ^ 2 ^H 5 C

^ - CO - CH - 0 «<0

are diapered as in Example 1 with the following formulation

40 ml of ethyl acetate,

10 ml of phosphoric acid tris-c-di-n-butylglyid, 100 ml of 5% gelatin solution,

30 ml of 4% acid latrium imdecylbenzenesulfonate solution. A homogeneous disperse is obtained which, after cooling, gels. The comminuted dispersate is then watered for hours to remove the Ääthylazetat ", laughs after melting b © i 40 ⁰ C and casting on a trans * parent undercoat is obtained after drying a clear layer,

15 g of a photographic blue-green coupler of the formula

-BH -C ₁₆ H ₃₃ ,

are analogous to Example 1 with the following formula theper

yells.

, 20 ml phosphoric acid monophenyl ester dipiperidide,, 120 ml 8% gelatin solution ,.

40 ml 4% sodium dodecylsulfate solution *

1 8 U

In dieseoj example, the removal of the low boiling Hilfslösungsaittele deleted _β The dispersed substance can immediately after the I & nulgierung be shed "

10 g of a photographic magenta coupler of the formula:

(-] j - HH ° »CO - (CHg) ₇ -CjH- C ₈ H ₁₇ 0 ~ CN Cl

are dispersed as in Example 1 with the following recipei ^;

30 ml of ethyl acetate,

10 ml of phosphoric acid di-ethyl ester ° dodecylamide, 100 ml of 5% gelatin solution, 20 ml of 8% sodium dihexylsulfosuccinate * After distillative removal of the ethyl acetate under reduced pressure at 60 ° C., a homogeneous disperse is obtained which after casting onto a transparent base and Drying made a clear layer

10 g of a photographic magenta coupler of the formula:

-NH - CO "<0> C _O H

O = C N NH - CO - CH

CcH ₁₁ Ct) 0 »cO /« Cr-H ₄ . (

are disper-.giert analogously to Example 1 with the following recipe;

40 ml of ethyl acetate,

12 ml phosphoric acid »n-octyl ester« to »[di» n »butylamide] 120 ml 6% gelatin solution

30 ml of 5% sodium diisobutylnaphthalene sulfonate solution · After dispersing, a homogeneous dispersion is obtained which solidifies after cooling. The reduced dispersion is then watered for 24 hours to remove the ethyl acetate. After melting

4O ° C and casting onto a transparent base, a clear coat is obtained after drying

Claims (4)

A process for introducing hydrophobic photographic additives into a hydrophilic colloid layer, wherein the additives are dissolved in an organic solvent which is not completely miscible with Y / aQser and are subsequently dispersed in the aqueous medium, characterized in that the high-boiling solvent ffiindenetans is a phosphoric acid triaraid of the general formula Rr 0 R1 i> ti / 1> N - P ~ -I \ and / or Phosphorsäuremonoesterdiamid the general formula nen? RA0 4 i P «. OR and / or phosphoric acid diester monoamide of the general formula N-P-OR7 ^{1 0R} 8
be used, wherein Κ .., R ^, R, _s R / »Rc * Rg independently of one another hydrogen atom alkyl, cyclohexyl ·" alkenyl, "cyclic radicals, phenyl", benzyl or substituted aryl, R ^ and R _Q alkyl, Cyclohexyl-, alkenyl-, alkoxyalky-, carboxyalkyl-, aryloxyalkyl-, chloroalkyl-, phenyl-, benzyl- or substituted aryl radicals and the number of carbon atoms ie of the substituents R ₁ Rp,. Ro "R ^ i Rc> Rg zu sam""· men 10 to 96 and the number of carbon atoms of the substituents R ^ and R _ß 2 to 40 is * 2 * Method according to item 1 _f, characterized in that optionally and independently of each other bound to the same nitrogen atom two substituents »
IL to Rg together with this nitrogen atom
form a cyclic radical, this radical
Ethylene imide, piperidine, partly or perhydrogenated
Quinoline, isoquinoline or morpholine is · 3 «method according to item 1, characterized in that in the substituents EL bia Rr the substituted
Aryl radicals benzoic esters contain 1 to 5 carbon atoms in the ester radical, and in the substituents R and Rg the alkoxyalkyl radicals groups having 1 to 4 carbon atoms in the alkoxy radical, the carboxyalkyl radicals having 1 to 5 carbon atoms in the carboxy radical, the aryloxyalkyl radicals groups having phenyl or chlorophenyloxy groups in the aryloxy radical and the substituted aryl radicals alkylphenyl having 1 to 15 carbon atoms in the alkyl radical or chlorophenyl mean « 4 «method according to item 1, characterized in that the high-boiling solvent in an amount of
25 to 200 %, based on the Zu zuperpergierenden Zu »is used _e Process according to item 1, characterized in that mixtures of different phosphoric triamides,
Phosphorsäuremonoesterdiamide or phosphoric acid di "·· esteroionoamide used v ^? _S ground Process according to item 1, characterized in that the phosphorsauretriaffii.de and / or phosphoric acid monoester diamides and / or phoephoric acid diester monoamides are used in a mixture with other high or low boiling solvents »