DE2063861A1 - Photosensitive, color photo graphic recording material - Google Patents

Description

Konishiroku Photo Industry Co., Ltd., 3-Chome, Nihonbashi-Muro-machi, Ghuo-ku, Tokyo (Japan)

Light-sensitive, color photographic recording material

The present invention relates to a light-sensitive, color photographic recording material having at least one A silver halide emulsion layer containing, in at least one layer, an ultraviolet absorber of the hydroxybenzotriazole type contains. These UV absorbers can be used stably in light-sensitive, color photographic recording materials containing silver halide be incorporated in order to improve the lightfastness of the color images obtained.

It is known that the color images formed by color development a light-sensitive silver halide-containing color photographic recording material, in particular They suffer from exposure to UV light and tend to fade when exposed to UV light are. In addition, color formers that contain in the emulsion layer of a photosensitive silver halide form color photographic material remains after color development, stains or veils of color under the action of UV light. To prevent the color images from being a Color photography fade / and due to the remaining

109827 / U69

If color former form spots, it is known to divide UV absorbers into one or more layers (e.g. light-sensitive Layers, intermediate layers, protective layers, etc.) of the light-sensitive color photographic recording material to incorporate. UV absorbers used for this purpose are generally said to be colorless or essentially be colorless and inert to other photographic additives and the various processing liquids. In addition, they should have excellent UV absorption and be stable to UV light. Of those so far known related UV absorbers, those of the hydroxybenzotriazole type are known as excellent UV absorbers become.

The hydroxybenzotriazole type UV absorbers develop theirs excellent properties in terms of UV absorption in general when made by the solvent dispersion method are dispersed in the layers comprising the color photographic light-sensitive recording material form. It is well known that the solvent dispersion method Can be effectively applied to a non-diffusing aromatic compound in non-crystalline form finely distributed and evenly dispersed in a hydrophilic binder. This method will carried out in that a non-diffusing aromatic compound to a high-boiling point which is difficult to mix with water organic solvents, optionally in a mixture with a low boiling solvent and then dispersed in a hydrophilic binder. Around In order to be able to use this solvent-dispersion method, it is therefore necessary that the UV absorber is of the hydroxybenzotrial3ol-type have excellent solubility in the above-mentioned organic solvents. the end For this reason it is therefore known to include an oleophilic group with a relatively long chain in the molecule of the

To incorporate UV absorbers of the Bydroxybenzotriazole type in order to to improve its solubility in the organic solvent. By introducing such an oleophilic group however, in the UV absorber, its molecular weight is increased; however, it becomes the basic structure for UV absorption not changed. Accordingly, such a UV absorber cannot exhibit the same UV absorbing effect as they do has been obtained before the introduction of the oleophilic group, unless the amount of UV absorber added is increased. However, if the amount of the UV absorber is increased, it causes coloring, staining or similar disadvantages.

On the basis of extensive research, surprisingly found that when using the compounds mentioned below according to the invention, an excellent one Effect of UV absorption can be achieved.

The present invention accordingly provides a photosensitive, Color photographic recording material with at least one silver halide emulsion layer according to the invention is characterized in that it contains dispersed in at least one layer a solution of at least a UV absorber of the hydroxybenzotriazole type of general formula

(D

109827 / U69

wherein R ₁ , R ₂ , ^R 3 » ^ß 4 ¹ ^ ^E 5 are each hydrogen or a halogen atom or an alkyl, cycloalkyl, alkoxy, aryl, carbalkoxy or alkylsulfonic acid

Group mean., _.

at least
in combination with / a compound of the general formula

(II)

wherein Rg and R "are each an alkyl, alkoxy or Mean acyl group; X stands for -00- or -000- and η is the number 1 or 2,

in a high-boiling organic solvent which is difficult to mix with water, optionally mixed with one low boiling solvent.

If a UV absorber of the above formula I in combination with a compound of the above formula II is used, the UV absorber has excellent solubility in water Difficult to mix high-boiling organic solvents or in mixtures of such solvents with low-boiling ones Solvents. According to the invention it is therefore possible to use such compounds of formula I in which the radicals R ^, Rg and R, a smaller number of carbon atoms have, so that when these UV absorbers of the Hydroxybenzotriaaol type are incorporated, thereby obtained light-sensitive, silver halide-containing

109827 / U69

photographic drawing materials are protected from this The photographic properties may change due to an increase * in the amount of UV absorber or the organic Solvent worsen. The UV absorbers can be recorded stably, and color images are obtained which have improved lightfastness.

So that the effect of excellent UV absorption occurs as far as possible when using the UV absorber of the general formula I, it is preferred to use compounds in which the groups E ^, Eg and Eg each have six or fewer carbon atoms, and the sum of the carbon atoms of groups E ^, E ₂ and E ^ being eight or less. A hydroxybenzotriazole type UV absorber containing such substituents having a small number of carbon atoms can be very easily dissolved in the organic solvents used in the solvent dispersion method, due to the presence of the compounds of the general formula II.

Table 1 shows the results of comparative tests. This compares the amounts required to dissolve 1 g of a UV absorber of the general formula I in a solvent, this solvent consisting of dibutyl phthalate alone or a 1: 1 mixture of dibutyl phthalate and a compound of the formula II is. The time given is in each case which is required in each case until the UV absorber separates out of the resulting solution if the solution is kept at 65 ⁰ O.

109827/1469

Dibutyl phthalate Farewell
dung s-
Time Table 1 Parting
manic
Time Parting
manic
Time need
did
lot Farewell
dung s-
Time 1: 1 mixture of ver
binding no. 16 and
Dibutyl phthalate Farewell
dung s-
Time I.
σι Solvent need
did
lot 3 min. 80 min. 85 min. 0.7 ml 85 min. need
did
lot 75 min. I. UV absorber
of formula I. 2.0 ml 2 min. 85 min. 90 min. 0.5 ml 75 min. 0.5 ml 83 min. link
number 1 1.0 ml 3 min. 1: 1 mixture of Ver. 1: 1 mixture of Ver
binding no. 8 and di-binding no. 11 and
butyl phthalate dibutyl phthalate 78 min. 82 min. 0.5 ml 85 min. 0.3 ml 80 min. link
Mr. 3 1.0 ml need
did
lot 1: 1 mixture of ver
binding no. 21 and
DibutylphthaJsb 0.5 ml link
No. 4 0.7 ml need
did
lot continuation 0.5 ml 0.5 ml 206386 1 0.5 ml 0.3 ml ^ Connection no. 3 0.5 ml VffrM Turing Nt? _r 4th Connection no. . I. i

⁷ '' !! II! ' ^I: "ι ■"■' ^! '"'''^1;"^;'■■■■■■ * ^; '''■,. ■■ - ■, ι, ,,,. ■ -

Table 2 shows the results obtained when the UV absorber was deposited
The time required was measured when the solvents listed in Table 1 are used in excess of the required amount.

109827 / U69

- Dibutyl phthalate Farewell
dung s-
Time Table 2 Parting
manic
Time. Farewell
dung s-
Time 1: 1 mixture of ver
binding no. 11 and
Dibutyl phthalate § Farewell
dung s-
Time 1: 1 mixture of ver
binding no. 16 and
Dibutyl phthalate Deposit
Time I.
03
I. 2063861 solvent lot 6 min.
8 min.
5 min. 1: 1 mixture of ver
binding no. 8 and
Dibutyl phthalate above
1.2 ml 120 min.
above
1.0 ml 120 min.
above
1.0 ml 120 min.
1: 1 mixture of ver
binding no. 21 and
Dibutyl phthalate over 120 min
over 120 min
over 120 min lot above
120 min.
above
120 min.
above
120 min. lot above
120 min.
above
120 min.
above
120 min, UV absorber
of formula I. 3.0 ml
1.5 ml
1.5 ml lot lot 1.2 ml
1.0 ml
1.0 ml 1.0 ml
0.7 ml
0.7 ml link
number 1
Vft-rhi TirhiTig
No. 3
link
No. 4
3 location 1.0 ml
0.7 ml
0.7 ml 1
3
4th Connection no.
Connection no. Connection no.
I.
I.

The compounds identified by numbers in Tables 1 and 2 will be mentioned later.

From Tables 1 and 2 it can be seen that a UV absorber of the hydroxybenzotriazole type of the formula I, the substituents contains a very small number of carbon atoms, and which has excellent UV absorption can be successfully and stably dissolved in a solvent can as it be for the solvent dispersion method is used. This is due to the presence of a compound of general formula II. If accordingly UV absorber of the hydroxybenzotriazole type general formula I for the solvent dispersion method in combination with compounds of the general formula II are used, the advantage can be obtained that not only the amount of organic solvent used is reduced, but the amount of UV absorber can also be reduced. The UV absorber can be stably dispersed without the risk of deposition, so that even during the manufacture and storage of a light-sensitive, silver halide-containing color photographic Material that contains these does not pose a risk of deposition of the UV absorber or the risk of coloration or There is staining caused by increasing the amount of UV absorber. Furthermore, there is no risk that the physical Properties of the emulsion layer obtained are deteriorated or the various photographic Treatment liquids due to an increase in the amount of the organic solvent used therein are prevented from closing the photographic emulsion layers penetrate.

- 10 -

109827/1469

2063361

Typical examples of hydroxybenzotriazole type UV absorbers of formula I are the following compounds:

(1) 2- (2'-Hydroxy-5'-methylphenyl) benzotriazole

(2) Butyl 2- (2'-hydroxy-5'-methylphenyl) benzotriazole-5-carboxylate

(3) 2- (2'-Hydroxy-5'-tert-butylphenyl) -5-chlorobenzotriazole

(4) 2- (2'-Hydro3qr-5-amylph.enyl) -benzotriazole

(5) 2 ~ (2 · -Hydroxy-5'-tert-butylphenyl) -benzotriazole

However, the invention is not limited to these examples. In principle, all UV absorbers can be of the benzotriazole type of formula I can be used effectively in accordance with the invention.

Typical examples of compounds of the formula II are in the following table 3 compiled. The connections too of formula II are not limited to these examples.

- 11 -

109827/14 69

2 O eT3 8

Tabel 3 R ₇ (OH) _n-1 X Substituents in
j? orrael II
Connection VT «6 4'-0CH _x 2'-0H -CO- (6) 4-0C ₁₂ H ₂₅ 4.-C ₅ H ₁₁
H 5'-OH -CO-
H -CO- (7)
(8th) 4-C ₅ H ₁₁
4-0C ₁₂ H ₂₅ 4'-0C ₄ H ₉
4'-0CH, 2 ', 5'-OH -CO-
2 ', 4', 6 K) H -00- (9)
(10) 4-OC ₄ H ₉
4-0C ₁₄ H ₂₉ 4'-COCH ₅ 2V0H -CO- (11) 5-C ₈ H ₁₇ 4 - COC ₄ H ₉ 2 ', 6'-0H -CO- (12) 4-0C ₄ H ₉ 3'-C ₅ H ₁₁ 2 ', 6'-OH -CO- (13) 5-COCH ₅

4-OC ₁₂ H ₂₅ 41-OCH ₂ - (^ - CH ₅ 2'-0H -CO-

(15)

₄ ._ _CO .Q. _C H ₅ 2 ', 6'-OH -CO-

- 12 -

109827 / U69

Table 3 (Ports.)

Substituents in
Formula II

Connection you%

(16) (17)

(18) (19) (20) (21) (22) (23) (24) (25)

3-OCH

5-0C ₈ H ₁₇

-OCH ₂

4-COCH

5'-OCH

5'-OC ₁₂ H ₂₅

4'-COCH

4'-0C ₁₂ H ₂₅

H -COO- H -COO- '-OH -COO- 2 ', 4'-0H -COO- 2

5'-COCH ₃

-COO-

2'-0H -COO-

-COO-

2'-0H -COO-

-COO-

2'-0H -COO-

- 13 -

109827 / U69

To convert the above-mentioned compounds of formula I and II into light-sensitive, silver halide-containing color photographic Incorporating recording materials can be the usual solvent dispersion method can be applied. For example, a light-sensitive, silver halide-containing color photographic recording material containing these compounds are produced in that a Mixture of the compounds of the formulas I and II in suitable proportions in a high-boiling point which is difficult to mix with water Solvent, optionally mixed with a low-boiling solvent as an auxiliary solvent dissolved, the resulting solution in an aqueous gelatin solution using a suitable surface-active By means of dispersing the dispersion obtained in this way into an aqueous gelatin solution to form a photographic Silver halide emulsion layer or another layer, and the resulting mixture then by the usual method for the production of a light-sensitive, silver halide-containing color photographic recording material is subjected. If a low-boiling solvent has been used as an auxiliary solvent, it can thereby removed so that the treatment is subjected to washing with water, which, after cooling, solidify and finely grinding the dispersion. The removal of the solvent can also be done thereby that the dispersion is heated or that the drying treatment is carried out during the preparation of the photographic recording material is carried out.

The silver halide photographic emulsion used according to the invention can any silver chloride, silver bromide and silver iodobromide emulsion. These emulsions can of gold or sulfur sensitization or • in a similar chemical bond and a color

sensitization. You can use stabilizers, Contain vehicles, hardeners, couplers, antifoggants, brighteners and antioxidants.

The amount of the UV absorber of the general formula I is expediently 1 to 15 mg / 100 cm ^ of the area to be covered. The amount of the compound of the formula II is expediently 0.1 to 2 parts per part of UV absorber. The amount of the organic The solvent required to dissolve these compounds is preferably substantially the same those of the compound of formula II.

The organic solvents used for the solvent dispersion. Method used can be the conventional solvents known for this purpose. Typical Examples of high-boiling solvents which are difficult to mix with water are di-n-butyl phthalate, benzyl phthalate, Triphenylpho sphat, tri-o-cre sylpho sphat, diphenyl-mono-pt-butylphenylpho sphat, monophenyl-di-p-t-butylphenylph ^ phate, Diphenyl mono-o-chlorophenyl phosphate and tri-p-t-butyl phenyl phosphate. Typical examples of low-boiling solvents are methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, ethyl propionate, carbon tetrachloride, Chloroform, methanol, ethanol, dimethylformamide, dioxane and methyl cellosalve acetate.

Light-sensitive, photographic recording materials with at least one silver halide emulsion layer according to the invention, prepared in the manner described above have the excellent properties mentioned at the outset and, if they are the usual color development are subjected to, they give color images that are a remarkable have improved lightfastness.

1 0 9 8 2 7 / U 6 9

The invention is further developed with the aid of the following examples explained:

example 1

A green sensitive gelatin silver chloride bromide emulsion, containing a magenta coupler was applied to a photographic Baryta paper applied and then dried to to produce a light sensitive emulsion layer.

Irrespective of this, 0.5 g of each of the compounds No. 8, 12, 17 and 23 of the formula II mentioned by way of example were added to 1 g of UV absorber No. 3. These mixtures were ocresylphosphat Tri-at 65 ⁰ C in a solvent mixture of 0.5 al and dissolved 3 ml Jtthylacetat and then 20 ml of a iO% aqueous gelatin solution containing saponin, given. The solutions were then dispersed using a colloid mill and then mixed with 15 ml of water. The obtained gelatin dispersions were coated on the above-described photosensitive emulsion layers as a protective gelatin layer so that the amount of UV absorber was 6.0 mg per 100 cm of the emulsion layer. Then it was dried. Samples 1 to 6 were produced in this way (sample 1 only contained the gelatin solution and sample 2 contained only the UV absorber).

After exposure, these samples 1 to 6 became the color development subjected, stopped, hardened, fixed, bleached-fixed and washed with water and then dried. The thus treated samples were measured for green color density by means of a photoelectric densitometer (mirror type) of the magenta image and the veil density of the non-image parts measured. Then the samples were subjected to the lightfastness test. Initially, the samples were direct

- 16 -

109827 / U69

Exposed to sunlight for a period of 50 hours by that their light-sensitive surfaces were set up to the south at an angle of 45 ° to the horizon. then the green color density and the blue color density of the thus exposed Samples measured again by the percentage (D / Do χ 100) of the density before irradiation (Do) to the density after irradiation (D) to be calculated. This percentage is known as the fade ratio. The results obtained are compiled in Table 4-.

109827/14 69

• To set the sample Tabel 4th Sunlight radiant ink Color veil
tight e nd
test State of
surface ι Prob added reduction
the green temp vd
test 0.20 Mr. lot delicacy
(D / Thu χ 100)% 0.05 0.18 unchanged No addition 55 0.05 0.05 matted 1 _ 45 0.05 unchanged 2063861 2 Tri-o-cre sylpho sphat ι ε
1.0 ml 87 0.06 3 UV absorber (3)
Compound No. 8 ι ε
0.5 ε 0.05 0.05 unchanged Tri-o-cre sylpho sphat 0.5 ml 89 0.05 0.04 unchanged 4th UV absorber (5)
Compound No. 12
Iri-o-cresylpho sphat ι ε
0.5 ε
0.5 ml 89 0.05 unchanged 5 UV absorber (5)
Connection No. 1?
Tri-o-cresylpho sphat 1 ε
0.5 ε
0.5 ml 90 6th
ι
QO
I. UV absorber (5)
Compound No. 25
Tri-o-ere sylpho sphat ι ε
0.5 ε
0.5 ml

From the results compiled in Table 4 it can be seen that when the sample contains the UV absorber alone (sample 2), it is dispersed in the solvent UV absorber has deposited in the form of crystals, so that the surface of the sample has become matt, and that the ability the UV absorption is worse in comparison with the samples according to the invention (samples 3 to 6) and bleaching of the color image and the formation of stains could hardly be prevented. On the other hand, the Samples 3 to 6 according to the invention show fading of the magenta dye and an increase in soleplate formation largely prevented.

Example 2

To a green-sensitive gelatin-containing photographic Silver halide emulsion containing a magenta coupler, was given a solvent dispersion obtained by doing that in the same way as in Example 1, the UV absorber no. 5 of the formula I and In each case the compounds Kr. 6, 13 »18 and 26 of the formula II were treated. The emulsions were then applied to photographic barite papers so that the amount of

UV absorber # 5 was 8.2 mg per 100 cnr. In this way Samples 7 to 12 were prepared (sample 7 only contained the emulsion and sample 8 contained only the emulsion UV absorber).

These samples were subjected to the development treatments described in Example 1. The green color density became the ban of the image part and the color soles eiälaSite of the white background measured. After 32 hours of irradiation in the Fade-Ometer using a Eofaleiibogen lamp the samples again densitometrically examined in order to percentage reduction of the green color density θ and the color

109827/1469

to measure haze densities. The results obtained are summarized in Table 5.

109827 / U69

sample
Mr. ι
ro Composition of the sample • Tabel "Pari Α-Οΐη" +: "τ" Τ-> "R-fcτ · η" Μ imcr Color sole i he
density nd
test State of
surface I.
ro
O 7th No addition reduction
the green temp
delicacy
(D / Thu χ 100) 90 vd
test 0.14 unchanged I. δ UV absorber (5)
Tri-o-cre syl phosphate added
lot 15th 0.04 0.12 matted 9 UV absorber (5)
Compound No. 6
Tri-o-cresylpho sphat _ 22nd 0.04 0.05 unchanged 10 UV absorber (5)
Compound No. 13
Tri-o-cre sylpho sphat 1 p
1.0 ml 88 0.04 0.04 unchanged 2063861 109 11 UV absorber (5)
Compound No. 18
Tri-o-cresylpho sphat 1 g
0.5 g
0.5 ml 90 0.04 0.05 unchanged B? 7 / 12th UV absorber (5)
Compound No. 25
Tri-o-cre sylpho sphat 1 g
0.5 g
0.5 ml 86 0.04 0.05 unchanged ΐ-
σ>
co 1 p
0.5 p
0.5 ml 89 0.04 1 p
0.5 g
0.5 ml

From the results summarized in Table 5 is it can be seen that sample 8, which contains a UV absorber alone, became matt on the surface as a result of the deposition of the DV absorber, and that in this sample the magenta dye noticeably faded and the stain was increased. Against it could for samples 9 »10, 11 and 12 according to the present Invention largely prevented the fading of the dye and an increase in the color haze of the background be avoided.

example $

A red sensitive photographic emulsion containing a cyan coupler was applied to photographic baryta paper. A photographic print was made on the resulting coating applied green sensitive emulsion containing a magenta coupler.

In addition, gelatin dispersions containing the substances listed in Table 6 were prepared. The production took place in that the UV absorber 1 of the general formula I and in each case the compounds No. 8, 14, 17 and 21 treated in the same way as described in example i became. The gelatin dispersions thus obtained were applied to the green-sensitive emulsion layers described above applied so that the Henge of the UV absorber was 0.5 mg per 100 cm ^. Then it was dried, whereby the Interlayer formed.

In this intermediate layer, a blue-sensitive emulsion was coated Bilberchloridbromid further containing a yellow coupler. This emulsion was added with a solvent dispersion having the same content as the above-mentioned gelatin intermediate layer, that is, a solvent dispersion containing a mixture of the

- 22 -

109827 / U69

UV absorber No. 1 and compound No. 8, 14, 17, respectively and 21 shown in Table 6, respectively. The application of the blue-sensitive emulsion was such that the amount

of the UV absorber was 10 mg per 100 cm. On the received A protective gelatin layer was applied to the emulsion layer. It was then dried. In this way, Samples 13 through 18 were made. (Where the sample was a so-called blank, which only has the gelatin interlayer and sample 14- had a layer that only contained UV absorber 1.) All samples produced in this way were the same treatments as described in Example 1, subject. The blue, green and red densities of the parts of the picture and the color density η of the white became Background measured. In addition, 50 hours of direct Sunlight irradiates in the same manner as described in Example 1. Then there were the densities again measured to calculate the percent fading of the individual densities and the soleplate densities. The results are compiled in Table 6.

1 09827 / U69

sample
TI τ » ι
ro Composition of the sample Table 6 to sunbathe green Red Dye veil
density vd
test i »X. added
lot Lightb « 45 59 vd
test 0.21 13th Sample with no gelatin
Layer and emulsion layer 49 62 0.08 0.20 14th UV absorber (1)
Tri-o-cre sylpho sphat 1 g
1.0 ml Ratio of diminution
the density (D / Do χ 100) 90 97 0.07 I.
0.09 g>
I. 15th UV absorber (1)
Compound No. 8
Tri-o-cre sylpho sphat 1 g
0.5 g
0.5 ml blue 94 97 0.07 0.10 16 UV absorber (1)
Compound No. 14
Tri-o-cre sylpho sphat 1 g
0.5 g
0.5 ml 47 93 98 0.07 0.10 17th UV absorber (1)
Compound No. 17
Tri-o-cre sylpho sphat 1 g
0.5 g
0.5 ml 53 90 99 0.07 0.11 ■ 18th UV absorber (1)
Compound No. 21
Tri-o-cre sylpho sphat 1 g
0.5 g
0.5 ml 92 0.07 2063861 96 94 93

From the results compiled in labelle 6 is It can be seen that in the samples according to the invention, the gelatin interlayers and blue-sensitive emulsion layers contained with UV absorber dispersions according to the invention, prevents the deposition of the UV absorber and the fading of the respective parb densities and an increase the staining was avoided.

Patent claims:

109827/1469

Claims (5)

Patent claims: Photosensitive, color photographic graphic recording material with at least one silver halide emulsion layer, characterized in that it dispersed in at least one layer contains a solution of at least one UV absorber of the hydroxybenzotriazole-Iyp the general formula (D wherein R ^, R2, R ^, R ^ and R ₁ - each represent hydrogen or a halogen atom or an alkyl, cycloalkyl, alkoxy, aryl, carbalkoxy or alkyl sulfonic acid group, in combination with / a compound of the general formula (II) - 26 - 10982 7/1469 wherein Bg and H ₁ -, each represent an alkyl, alkoxy or acyl group} Σ represents -CO- or -000- and η is the number 1 or 2, 2. Recording material according to claim 1, characterized in that that it is the UV absorber of the formula I in one ρ contains an amount of 1 to 15 mg per 100 cm of the layer. 3. Recording material according to Claims 1 to 2, characterized in that that it contains the compound of the formula II in an amount of 0.1 to 2 parts per part of UV absorber of formula I contains. 4. On drawing material according to claims 1 to 3, characterized in that that it contains the compounds of formula I and II in the top layer of the recording material. 5. Recording material according to claims 1 to 4-, characterized in that that there are the compounds of the formula I and II in at least one layer of the light-sensitive emulsion layers contains. Dr.T / pf 109827/1469