DE1447668A1 - Photographic material with additives that prevent color clouding - Google Patents

Description

ΐη, ΐα .. '

öhaehin film £ abuahi.kl Kaisiia, 21o iiakanuma,. ^ Inamlawiiigax'a-aachi » Ashigarakami-gun, Krtnaftawa-ken, Japan

Photographic material with color haze preventing / iusdtsen «

The invention relates to color photographic processes ixuibes ^ aiier · those where the color couplers approach photography Äterial be incorporated and a. tcolor triibuses preventive3 means applied

are known color photographic materials that Contain coloring substances, some by reaction with oxidation products of the as! color developer used * adLet * & Κ, Ι-Dialkylparaphenylenediamines produce colors.

For this purpose, 5 * coupling agents with oil-soluble radicals are used in • an "old water immiscible high-boiling organ!" Also dissolved, then in aqueous gelatin oil alt Smulgatorerx, like Hatx'lumalkylbenzolsulfonat dispersed and in this in the order of the halogen aluminum emulsion * ug »eet * t»

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Bs are also oil-soluble couplers in the photographic Emulsion mixed in and coated with it without being in a high-boiling point that is immiscible with water organic solvent is dissolved.

There are also couplers that have long-chain aliphatic hydrocarbon radicals and in their molecule contain a water- or alkali-soluble radical, mixed into the photographic emulsion.

, ie with such color photographic materials, color clouding often occurs in the image, i.e. the purity and The clarity of the color is weakened and its brilliance is lost. These weakenings of purity and Color saturation are here briefly referred to as turbidity. The reason for these defects is that after developing and bleaching, the removal of the bilbera is incomplete. JSin broad Idciataba absorption band of the silver is superimposed on the narrow absorption band of the developed color image.

It has now been found that the silver removal is extremely successful and color clouding in the developed image is largely avoided if a vinylpyrrolidone polymer or mixed polymer is incorporated into the color photographic material »especially when using a photographic emulsion which contains oil-based couplers and high-boiling oily solvents. BATH

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A suitable colloid such as gelatin or polyvinyl alcohol can be used as a binder for the photographic emulsion or its derivatives, polyacrylamides or their derivatives, cellulose derivatives, casein, alginates and the like are used will. Gelatin is the most preferable.

The additive according to the invention is a vinyl pyrrolidone polymer or mixed polymer of vinyl pyrrolidone and e.g. vinyl esters, acrylic acid esters, methacrylic acid esters ^ Acrylic acid, methacrylic acid or styrene. Vinyl esters are e.g. vinyl acetate, vinyl propionate, vinyl

AIs
butyrate. Examples of acrylic acid esters are the methyl, ethyl, butyl and 2-ethylhexyl esters. The effect of the copolymers depends on the monomer ratio. For example, with a vinylpyrrolidone / vinyl acetate copolymer, the best effect is achieved with a monomer ratio of 7o: 3o.

According to the invention, polymers can be used which are colloidally soluble in water or alkali. Preferable are those which are in organic Solvents are soluble. With different degrees of polymerization Slight differences in effect were observed. If the polymers are solids or Ideal liquids boiling above 2oo * C can be used, the polymer grade can be used. The transparency in the lace or glanelioht it is so much the better, the higher the degree of polymerization · - ^

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To see Eimii of the polymers in the photographic Emulsion can: the following organic solvent [; c-iiiittel vex · - be applied:

Alcoii oils such as methanol, ethanol, isopropanol, Cellusolve, Oarbitol. ^ .ster uie ethyl acetate, butyl acetate, ether such as Ethyl ether, ldoxane, tetrahydrofuran, ketones such as acetone,

E, ... rnides such as lactams, dialkyl carbamides.

The amount of additive to be mixed in depends on the weight and weight of the hupijlör contained in the jihnulsion. In general, the highest effect is achieved when the addition of lolymoris is about 5% by weight, including on gelatin. However XCR can also be higher, "hen the addition of 25 ^r, ö exceeds the ilntwicklungswirksamkeit be and ivieinbraü-" biw. coating properties deteriorate. In most cases, therefore, an additional ief of etv / a 5 to 12% zweckmäeeig.

The invention is applicable to all types of color couplers. Particularly good results have been obtained with filing Couplers achieved:

4-Ben8oylacetaido-N-butyl-N ^ octylbeneaaid

COCH ₂ OOlIH ■ // Y> - C0N \

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U47668

-Chlor-II-dodecyl ^ -naphthamide CB

- GONH (OH ₂

Cl
Ir. 3

deoanaiiido) -propanamido) pyra »olin-5-one

Cl 91 · 9 »rtotrübujME rertiinderaA ·» Poly »· ri» At ·

Zuianmen-

or beiro BeBch.icht "n augege" bea «• approx. Aa btsteii asked me to add «during the

Pt · «rfl» dQBC «g« BäaMn Zu * ät »e can la one shift $ M 'Mlfim od ·» all · »Sohlofctra W« «» .B. also that

· In the lMitem Wl came »41 ·

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! ^ given · amount 75 % »related to gelatine, without this having an unfavorable influence on the quality of the film and the coupling effectiveness.

Further details of the invention are illustrated in the following examples.

Example 1

4 g of coupler no. 1 mentioned above and 0.8 g of a vinylpyrrolidone - vinyl acetate and mixed polymer, ⁶ volume ratio 7 '* 5) were dissolved in Ί.2 ecm libutyl phthalate, 3 ecm ethylacetate and 0.8 ecm xaopropanol at a high temperature temperature resolved. This solution was added to the 10% above aqueous gelatin solution, which contained 2 ecm of an above aqueous solution of sodium alkylbenzenesulfonate, and stirred at 40 to 50 ° C. for 3 minutes in a high-speed homogenizer. Stirring was interrupted for one minute "then" repeated "5 times a year, resulting in an emulsified dispersion of coupler" polymeric acid and gelatin ". This dispersion was smeared with an emulsion containing 4.5 g of silver bromide and 5 g of gelatin and used on the coating. Laughing and interior development was treated with potassium ferricyanide bromide washed with water and bleached.

1 * 1 to the Sslbkupplsr the dullness was sgr "* 4 * 8 Qelbs

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determined by measuring the optical red density. The results are shown in Table 1.

Example 2

With otherwise the same working method as in example 1 instead of the coupler Mr. 1 2.4 g of the coupler. 2 used.

In the case of the cyan coupler, the degree of fogging became through Measurement of the optical yellow density determined. The result is shown in Table 1.

Example 2

With otherwise the same procedure as in Example 1, 4.3 g of Eupplere were used instead of the coupler Fr. 1 Mr. 3 used,

With the purple coupler, the degree of turbidity was determined by measuring the optical red density. The result is shown in Table 1.

the? febelle * shows that the opacity (op-density in an undesired wavelength range) is considerably reduced in all couplers by adding the named polymer *.

^ ₁

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Table 1 Hot density Yellow density o.75
O.16 Luppler lolyvinylpyrrolidone
Polyvinyl acetate
(Mol. Ratio 7 J 3) o. 93
O.48 number 1
applies » without addition
with addition o.6o
O.27 - · No. 2
(Cyan) without addition
with addition Mr. 3
(iüiagenta) without addition
with addition Beisifel 4

With otherwise the same procedure as in example 1 were used as additives according to the invention in eight others Samples of the polymers listed below were each used in an amount of ο.8 g.

Sr. Jir. ITr. Mr.

1 polyvinylpyrrolidone

2 tinylpyrrolidone - ivuethyl acrylate

3 ¥ inylpyrrolldon - Aethylaerjiat 4l · vinylpyrrolidone "B" tyl acrylate

Aatfliara Chemioal Co.)

Mr. ? ¥ 1

ilonomerenvera

7 * 3 7 ι 3 7 * 3 7 s 3

1 s 1

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Since a yellow coupler was stored »Table 2 shows the measured hot density for assessing the degree of turbidity.

Table 2

Polymer number 1 No. 2 No. 3 No.4 No. 5 Kr. 6 Br. 7th Sv.8 0. To
sentence Coupler ο 3ο 0.50 0.34 0.42 .. * 5 0.23 0 0.50 0.75 Kr 1

L'ie! Table shows that the optical red density and hence the degree of turbidity for all additives is significantly lower than for the comparison sample.

Example 5

The same procedure was followed as in Example 1, but the dibutylplithalate was omitted. In the test, the red density was o.2o, while it had a value of o.95 for a comparison sample without an additive according to the invention.

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Claims (1)

Claim Color photographic dialogue silver material characterized by a content of a polymer or mixed poly beriaat, the vinylpyrrolidone as a discoloration preventing? ^s ittel. 809902/0708