DE1643516A1 - High-boiling organic crystalloid solvents for water-insoluble or only sparingly water-soluble chemical additives for photoemulsions, in particular color couplers, and photographic emulsions containing such solvents in a finely dispersed state - Google Patents

Description

The invention does not relate to a new class of crystalloid organischejf solvents that _t can be used especially well, or only slightly water soluble chemical Hilfszusatisstöffe after the so-called ⁱ Bi8pQrsionsverfahren "oinzuverleiben photographic silver halide ₉ in particular Iäniulsionen.

There are a large number of different chemical auxiliaries ss stoffe * the aich photographic emulsions with the help of the Incorporate dispersion process, but this is

. BAMK ACCOUNT DiUJiCHE RANK AO MOHCHtN. HOPOLDiT (I, 7t »KTO.

109827/180 3 _{R. n ΛβΙΛ}

BATH ORIGINAL

x'aliron aeist üasu öenütKt, the pact "graphic emulsions as Jfcrbkupple? sie]: a.ru ".ten" Iteaisolion _ auxiliary sus & tsefcoffe silver-.haiog = 53ild®mulaloi.ien oiBsuverlsifosii. · - from which photograpixisühss material for the Parbpfeoto / r.iraphis is made wi.rcL

Me colored pictures in pJSiotographisiihem material of this 2yps ent are known to exist oli d.urs? ii Heafetion of the color couplers with dsition products das Farbontwi ^ lilor-Sr.

e Ma - 3i ^: ia, l är.fr ^ es' fljrpa contains in the Hegel three sinv- your, sensitive lißiulsionsschiekteii., which in the three spectral areas Β1βλι- _; dirJii and hot ssnsensibilized

Jade Schi eilt contains at least one color coupler _ε which, through the binding of the oxidized jirripni ^ lu.exs, provides a purple or blue-green color image,

For several reasons, as a rule, it is expedient that the chemical auxiliary substances are stored in the individual emulsions in a diffusion-proof manner and bulky au mackea- by long saturated ©, liphatisehe chains generally having 12 to 18 carbon atoms introduced into the molecule "this however took the Wassörlöslichlceit the Hilfszxisatz;?. equipment and materials _{considerably.;.}

109827/1803

"i r BAD ORIGINAL

. ^ 5 ~; 16A35.16

To solve the problems resulting two verschiedeneWöge label * were One inspects the fact that one = formation in the HilfszusafssstOff- (color couplers ") ~ acid molecule _g of salt * functional groups einführt- Such Hilfseu" can then satsatoff In aqueous 'Alkali solutions are dissolved and incorporated in this form into the hydrophilic colloid of the photographic emulsion.

The widely used method is the so-called dispersion process. In this case, predominantly lipophilic color couplers or auxiliary chemical additives are used, which are dissolved in a crystalloid, organic, high-boiling liquid that is immiscible or only slightly miscible with water. which a high solubility for the color couplers and a good permeability for the developer BZV / ₀ whose Oxy & ationsprodukte has _o The solution of the color coupler in this crystalloid solvent is then emulsified by means of homogenizer in water _B which a wasserdurehlässiges hydrophilic colloid of the in the production of photo = - emulsions usual manner and optionally a sharpening - medium containing 3cann _e -

The dispersion thus obtained of extremely small _t the droplets of the solution of the color coupler in the crystalloid Lösun-äsmittel is disclosed in "are evenly distributed water phase can then be easily incorporate the photographic emulsion *"

A class of compounds has now been found which can be found in the Dispersion refractories are particularly advantageous as a crystalloid solution.

1098 27/18 03

ίΠΟ <&& \ BAD OFHGlNAL

- 4 - '16A35 16

use medium. permit,,

The photographic material of the _p these crystalloid .Lösungsmittel is prepared according to the Uispersionsverfahren using, besitat excellent properties, in particular, the image sharpness = halide color photographic material is large than the one who * ™ ,. which can be achieved with photographic material which is produced using known crystalloid solvents after the dispersion process "

The invention thus relates to organic crystalloid high-boiling solvents, the formula

R --C - O - (CH) "- CH - $ * '(1)

OXY & ^c

in which R is a straight-chain or branched C ^ _ ^ g => alkyl radical and η is less than or equal to 6 iat _f

X and Y are identical or different and each is a hydrogen atom or an alkyl radical are ^

ß ^{n is} a straight-chain or branched acyl radical with 1 to 18 carbon atoms and "■ -.-" H ^{8 is} a hydrogen atom, _{r is} an alkyl radical or a mono-valent radical of the formula

K-C-O- (CHL - CH - ■ (II)

It. C ^X1 - t -

OX Y

istf in ii _t . X _? Y and η as defined above have ₀

109821/1003

BATH ORIGINAL

a ·, * Y ε »-

These compounds are mostly liquid at room temperature; also üiejenigen Verbindungeng in the pure state, not liquid sinds form with the color couplers liquid at room temperature systems _o besitaen fairly high boiling points above 175 ⁰ C at atmospheric pressure and evaporate, hence the following drying layer on the casting of the plxotographischen emulsion not .if "Furthermore, they are not only very light = and heat resistant, but have ausserdera good permeability for the Oxydationspro = products of the color nt winder "the solvents of the invention be" = a sit beyond one the well-known so far, kristalloideiL solvents ₉ S ₀ B ₀ .Bibutylphthalat . " Tricresyl phosphate or Laurinsäuredibutylamid (cf. Italian Patent No. * »432885) j superior Lösungsverinögen _s which permits the amount of 30 required amount to be used in relation to the known when using crystalloid solvent bit 50 i» herabausetζenο

The cause of one of the greatest disadvantages of the dispersed parbo-coupling system is the presence of the crystalloid solvent in the photographic emulsion layer, which leads to difficulties in sensitization _for increased acidity and to a deterioration in adhesion According to the invention, these disadvantages can be substantially reduced or "can even be completely eliminated" if the amount of the crystalloid solvent can be reduced considerably ". The reduction in the amount of solvent used as a result of the invention offers the further advantage ₉ that it reduces the "layer thickness * and thereby improves the sharpness. It was also found that with photo" * ·

| 0a BAD ORIGINAL

Graphic material eiaa crystalloid solvent according to the invention contains ₈ - no yellow scuff formation occurs during storage ».

Some compounds which can be used as crystalloid solvents according to the invention are listed in a table below. In the third column of the table lists the values of the solution relativan ^ / erxnögens of each compound are shown ₀ The number listed is that amount of the solvent in ral to "which is required to. at TC ⁰ O bring a -jramm of a common, as standard geiionime.v_en 3? arbkupplers in solution au, *

In! Table also three known crystalloid solvents are Yergleioh aufgeführt- _s with _a? b and c are given as "

BADORiGlHAL

1) Ethanolamine caprylate caprylaiaid

Sahelle

J.g-OH-

ml of solvent sur Xiösung τοπ, 1 g elaes ubCli-- · chen;

Xers

Propanolaiaiaiaobutyratisabutyramlcl

(SO ■ ΛΑ.

CH,

CH

! CH-COO-CH ₂

'.nn Wu ™,

S) I-Methylethanolainincaprylateaprylamid CH ₅ -CCH ₂ ) ^ - OQO-CH ₂ -CH ₂ -li-CO- (CH ₂ ) g * -CH-,

6) iithylathaJaolamine capryXatv-japrylamid 0
CH

CH ₂ ) _& -C00 ^ CH ₂ -CH ₂ -l-C0- (CH ₂ ) # ■ -CH,

C ₂ H,

2 "6

mL of solvent to the solution of 1 g of a conventional color coupler at 7O ⁰ C

Diethanolamine dibutyrate butyramide (CH ₃ -CH ₂ -CH ₂ -COO-Ch ₂ -CH ₂ -) ₂ Ii-CO-CH ₂ -CH ₂ -CH ₃ 2.8

3) Diethanolamine dicaprylate caprylamide

2 _fl ?

: < } Diethanolamine diacetate

{CH ₃ -COO-CH ₂ ^ CH ₂ -) ₂ BH

Ι ·:} Biethanolainindiacetate palmitoylamide, (CH ₃ -COO-CH ₂ -GH ₂ ") ₂ K- _r GO-CH ₂ --C ₁₁ -H ₂ 9

2 "9

j. ") Biisopropanolaniindibutyrate dibutyramide (CH ₃ -CH ₂ -CH ₂ -CQC-GH ₂ -Ch-) 2JI-OO-CH ₂ -CH ^ -CH ₃

2.7

r> 00 S ο

CD OO

cn

CD

GH ₇ ,

Diisopropanolamineicaprylate caprylaüiiü (0Ηχ- (GH ₂ ) $ - 0ΟΟ- = 0Η2-0Η

ml solvent sur solution of 1 g of a UbIi- * chen Parbkupolers at 70 ⁰ C

ithanolpropanolamine dibutyrate butiTamia

£, C d

a) bibutyl phthalate (at 100 ° C)

Is} Tt ic re s jlpho sphat

Mbutyllaüramiö

to

* - »■■ CD

■ '% to 5 ρ 2

09

ίο - ■. -.

Usually change in the production of photographic systems Material, auxiliary additives used dissolve in the inventions Suitable crystal solvents are just as good.

The crystalloid solvents according to the invention can be easily and with high yield by reaction described _{by R 0} M ₀ Silverstein and coworkers in <T _a Am ₃ Oil Chemists ³ Soc Vol _{0 52 (1955) »pages 354-356} of an amino alcohol with the stoichiometrically equivalent amount of a free fatty acid without one ». Produce catalyst,) The connections iir ο 5 _f 4 ,, 5 »6 _? 7? Q _t 11 and 12 of the table are prepared in an analogous else _t V / as the compounds of preparation is described below:

jgjjg ;, the connection ;, ßr _{| 9} . 3j, Xth ^ In a four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 30j5 g (0 ₉ 5 mol) of ethanolamine are dissolved in 100 ml of xylene, whereupon the solution from the dropping funnel quickly 14 be -4 g (1 mol) of caprylic acid is added "During the addition of the acid the temperature rises tem- = · in the flask at 70 to 80 ⁰ C ₀ Once the addition of the acid is complete, the reaction mixture to 16o ° C is heated to about Maintained at this temperature for 2 1/2 hours * The xylene distilled off together with 17-5 ml of water of reaction (theory 18 ml) /

Subsequently, the reaction mixture is allowed to cool to room temperature whereupon it is poured into a funnel, in dom 400 ml of Mäthylätner are presented »The Itherlösuiig is three-

1098 277t803

times with 10 ml. Washed three times with water until the reaction is neutral. The ether solution is then dried with 20 g of anhydrous sodium sulfate for 24 hours, then filtered through a folded filter to remove the sodium sulfate and finally evaporated on a water bath is distilled under reduced pressure “The first ^{runnings which pass below half 100 °} C. are discarded, ₉ whereupon the distillation is continued with a further reduction in pressure. 137 * 5 g of a pale straw-yellow oil with a boiling point M of 150 ^{° are obtained} C / 1 Torr «Yield: 37 % of theory.

Establishing the connection Mr. 9 »Diethanolamine iaindiaoetat In a 2000 ml four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 105 g of diethanolamine are dissolved in 300 ml of benzene. This solution is slowly mixed with 120 g of glacial acetic acid from the dropping funnel« The reaction mixture is then left to boil for 4 hours, whereupon the benzene is acidified under normal pressure and then distilled off under reduced pressure. Finally, one catches 148 g of product with a boiling point of 182 Ms 184 ⁰ O / 15 Torr to _o Yields 78 ^.

Production of the V erbindu ng Ur ₀ 10 χ Diäthan olamindiacetat · "

palmitoylamide

In a 2000 ml _{four-necked flask equipped with a stirrer P,} a reflux condenser, a dropping funnel and a thermometer and protected against moisture ingress, 138 g of the compound Mr * 9 are dissolved in 600 ml of dry dioxane

109827/1803

BATH ORIGINAL

and then 131.2 g of jyridine are added. 200.4 g of palmitoyl chloride are then added from the dropping funnel at room temperature , washed with water until neutral and then dried under reduced pressure. This gives 202 g of crude product of melting point, 54 to 59 ⁰ G, After recrystallization from 300 ml acetonitrile, 175 g of pure compound are ο of mp 57 to 59 ⁰ C obtained »yield? $ 70 >,

Preparation of Compound No. 1 ?; Ethanolpropanolamine ~ dibu t yratbu tyraiaid

In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer four-necked flask are 29 ₉ 8 g iithanolpropanolamin dissolved in 100 ml of xylene. The / solution is mixed with 66 g of butyric acid and then heated to 140 to 150 ° C. After one hour, xylene and water are started to be distilled off. QC ml of xylene and 10 ₃ 5 ml (! Theory % 13.5 ml) of reaction water pass over within 4 hours. The reaction mixture is then allowed to cool to room temperature and it is poured into 300 ml of diethyl ether. The ether solution is in a separatory funnel three times each with ^ e ICO ml of 10 $ »hydrochloric acid _s of water and 5 ^ acetic liatriumcarbonatlösung and schliesslieh again washed with water until neutral * The Ätherlösuiig is treated with 10 g anhydrous sodium sulfate, _p dried for 24 hours then filtered sur JSntfernung the sodium sulfate by a Baltic filter and finally evaporated on a water bath, the "RÜcltetpnd is under comparable - ■ 1098277 1803 _{BAD 0R, elNAL}

distilled under reduced pressure. The 10O ⁰ G portions are discarded, whereupon the distillation is continued while the pressure is reduced. One rhslt 50 g of product with a boiling point from UOQ to * SOl ⁰ G / Jorr «yield

The dispersions are prepared in a known manner in a colloid mill or a similar device, it being possible to add emulsifiers. Sometimes it may be massive, the dispersion in water or ± n an aqueous% solution of a natural or synthetic wasserperme expedient ^9; ablen hydrophilic colloid "sB, Gsiatins, Pclyvinylalkohol or agar-agar, by Zugab® Sinea stiedsig @ iedead @ n HilfslÖsungsiaittels , ZoB. Easigsäureäthyleeter odt »BtttylQSter, liersstellen *

To Herat RECOVERY Di spereioaen with gewünsehteii photograph - see properties ka & a it in ^ iΐ / len cases be advantageous to use mixtures of two or more crystal olden solvents to be used · For example, sin erfinduiigsgemaseea krietalloidee λ

Combination with a known solvent can be used ₉ by the d @ r Brfshungsiaddx ;: or other physical properties «dss? riispereioii gaänd-a ^ t can be. ν ■ ". ': - ■■ ^{-::: Γ:} ■.';'.. y /.''■..

In the Diepereipneverfahren can only
to be used before "the feil / laity temperature is liquid." Seim Diapergieren in water or a hydrophilic colloid is the wäisrigsn Oenisch ausserordentlioh small droplets "the

contain the color coupler «These dispersions are quite stable and permeable to the usual photographic baths» The dispersions of crystalloid solvents according to the invention with color couplers or other chemical additives dissolved in them can be added to the usual gelatine »silver = · halide-iäBUlsionen» their protective collpid as already _mentioned} Gana or may be replaced by other hydrophilic colloids such _e B "polyvinyl alcohol or agar-agar in part, incorporate without difficulty.

To illustrate the invention, the following is the production some photographic emulsions or some such emulsions Described dispersions to be incorporated of color couplers dissolved in crystalline solvents according to the invention.

example 1

Ig of a purple coupler of the formula

CH ₂ - ~ 0 - NH - CO - SE - {/ \ - SO ₂ KH - V ^ y ~ ^C 12 ^H 25

is dissolved in 2 inl of Compound No. "7 dissolved by heating to 100 ⁰ C overall>" The hot solution is poured into 20 ml giner 4? S-gelatin solution which contains 2 ml of 10 $ strength Hatriuiiitetradecylsulfatlösung. The equipment is emulsified in a hoofiogenizer and then incorporated into a silver halide emulsion. This emul ~

• ^, y-w - '. ■. ■ -.- BADORiGINAL

"^" "^ 1098 27/180 3

Sion is poured onto a suitable carrier material and dried. The photographic material produced in this way is sent to » finally exposed and then color developed in the usual way, bleached and fixed. You get a purple one haze-free image with good sharpness *.

Example 2

1 g of a purple coupler of Pormel

CONH

is dissolved in 2 ml of Yerbindunjg Kr ₉ 5 of the table by heating to 100 ⁰ G. The hot solution is poured into 20% of a gelatin solution containing 2% of a 10% Katriuratetradecylsulfatlösung. The mixture is emulsified in a homogenizer and then incorporated into a silver halide emulsion. This photographic emulsion is cast on a support, dried, exposed to light, color developed, bleached and fixed to give a purple-colored image

Example 3

1 g of a purple coupler of the formula

CH ₅ , C - NH - CO - HH - ff vS -SOo-HH- ff \ S -CH

• ² V- / ² W / 12 25

is by heating to 7O ⁰ C in 0.5 dissolved the compound No. 8 of Table 4 ml ml of ethyl acetate.. The solution is poured into 20 ml of a 4 μg gelatin solution which contains 2 ml of a 10 μg sodium tetradecyl sulfate solution. This mixture is emulsified in a homogenizer and incorporated into a silver halide emulsion. By pouring the photographic emulsion thus obtained onto a support and then drying it, a photographic material is produced which is exposed, color-developed, bleached and fixed, whereby a purple-colored image is obtained.

Example 4

1 g of a cyan coupler of the formula

is dissolved by heating to 10O ⁰ C in 2 ml of the compound no. 3 of the table and 4 ml of ethyl acetate. The solution is poured into 20 ml of a 4% gelatin solution, which is 2 ml of a

109827/1 * 0 ^ BAD ORIGINAL

20 # sodium tetradecyl sulfate solution contains »The mixture is Homogenfert in a homogenizer and then a silver halide emulsion incorporated ", by pouring the so herg * - Fltellen photograph! see iiimulsion on a carrier material and Drying of the layer gives a photographic material which exposed, color developed, bleached and fixed, resulting in a blue-green image »

Example 5

1 g of 2'-phenyliraino-3'-tetradecyl'-5-benzal-4-thiazolidone of the formula

^C 14 ^K 2 <T * - ^C0

~ N β C Μ = CH

is 0.2 in the compound No. 10 of Table 2 ml of ethyl-Bäureäthylester ml. Jrhitaen by ar.f 50 ⁰ C dissolved. The solution is poured into 20 ml of a 4% gelatin solution. which contains 2 ml of a 10 i) 6 strength sodium tetradecyl sulfate solution *

The mixture is emulsified in a homogenizer and can then be incorporated into a silver halide emulsion or other light-sensitive layer. "

109827/1803 ® ^ ^D original

Ex a mp 6

1 g of a compound of the formula

0 - C ₈ H ₁₇

is dissolved in 0.2 ml of compound no. 10 of the table and 2 ml of ethyl acetate by heating to 50 ^° C. The solution is poured into 20 ml of a 4% gelatin solution "which contains 2 ml of a 10% sodium tetradeoyl sulfate solution" The mixture is emulsified in a homogenizer and can then be incorporated into a silver halide emulsion or other light-sensitive layer

Claims

109827/1803

BATH ORIGINAL

Claims (1)

Claims I ₀ crystal oils, organic high-boiling solvents of the formula I ECO- (CH) _n - CH - ' OXY ^R ' in the R a straight-chain or branched 0 i ^ iß ™ Alkylreet η is less than or equal to 6, X and Y are identical or different and each is a hydrogen atom or mean an alkyl radical, H "is a straight-chain or branched acyl radical with 1 to 18 Carbon atoms iat and fi ^e a hydrogen atom _t an alkyl radical or a monovalent Heet the formula (CH) ₇₁ -CH 5 η j Ο- is _? in which H _P X _P Y and η have the meaning given above _β 2c Photographic, at least one or only echwer water-soluble chemical auxiliary additive _t particularly a • color coupler dissolved in a high boiling organic crystalloid solvent, containing in finely divided form emulsions "or" layers _f characterized in that they organic than hochsiadendes 109827Π803 _Λ ,,. ;; ■■, · _v: BAD OFHGlNAL crystalloid solvent contain a compound of formula I » 3ο Photographic emulsions or "layers according to claim 2" characterized? that they are considered photosensitive Substance containing at least one silver halide 4c Photographic material, labeled by at least one emulsion layer according to claim 3 ° 109827/1803 BAD ORiGtWAL