US3676139A - Color photographic printing paper - Google Patents

Abstract

A COLOR PHOTOGRAPHIC PRINTING PAPER CONTAINING AN ULTRAVIOLET ABSORBENT AND A FLUORESCENT BRIGHTENING AGENT REPRESENTED BY THE FORMULA

X-((4-R1-S-TRIAZIN-1,6-YLENE)-N(-R0)-(3-(M-O3S-)-1,4-

PHENYLENE)-CH=CH-(2-(M-O3S-)-1,4-PHENYLENE)-N(-R0)-(4-R1-

S-TRIAZIN-2,6-YLENE)-N(-R2)-Y-N(-R2))N-X, AND X-((4-R1-

S-TRIAZIN-2,6-YLENE)-N(-R0)-(3-(M-O3S-)-1,4-PHENYLENE)-CH=

CH-(2-(M-O3S-)-1,4-PHENYLENE)-N(-R0)-(4-R1-S-TRIAZIN-2,6-

YLENE)-N(-R2)-Y-(Z)-Y-N(-R2))N-X

Description

# d States Patent 01 3,676,139 Patented July 11, 1972 7 The portion of the term of the patent subsequent to Oct. 26, 1988, has been disclaimed Int. Cl. G03c 1/92, 1/84 U.S. Cl. 96-82 9 Claims ABSTRACT OF THE DISCLOSURE A color photographic printing paper containing an ultraviolet absorbent and a fluorescent brightening agent represented by the formulas the solution to dye the gelatin with the fluorescent brightening agent. However, this method has the disadvantage that it is diflicult to dye selectively a necessary layer with a fluorescent brightening agent. In addition, an additional processing bath containing the fluorescent brightening agent is required.

There has also been proposed a direct-addition method, in which a fluorescent brightening agent is added directly as an aqueous solution 01' an organic solvent solution thereof to an emulsion or a dispersion for a photographic silver halide emulsion layer or to a supplemental layer. An indirect methd has been proposed, in which a fluorescent brightening agent is dissolved in a solvent having a high boiling point (or a mixture of a high boiling solvent and an auxiliary solvent), the solution dispersed in an aqueous gelatin solution, and this dispersion added to a photographic light-sensitive emulsion.

However, since the known fluorescent brightening agents are usually low molecular weight compounds, when they are incorporated in photographic emulsion layers or sup- The present invention relates to a color photographic printing paper containing a fluorescent brightening agent and an ultraviolet absorbent. More particularly, the invention relates to a color photographic printing paper having a photographic layer containing a watersoluble, fluorescent brightening agent having an anti-diffusion property to fluorescent-whitening and an ultraviolet absorbent to prevent fading and stains caused by ultraviolet rays.

The whitening of photographic printing papers has previously been accomplished by a method comprising adding a fluorescent brightening agent to the baryta layer of a baryta paper. However, even if a baryta-coated paper is whitened by the aforesaid conventional method, the whitening effect is lost in color photographic printing paper, since such papers must also contain a compound capable of absorbing ultraviolet rays, such as, ultraviolet absorbent and a coupler.

Therefore, various suggestions have been made to supplement the whitening effect thus lost. For example, there has been proposed a method in which a water-soluble fluorescent brightening agent is incorporated in a processing solution and a gelatin-containing layer is processed by plemental layers, the greater part of the fluorescent brighteningagents is diffused out during processing and washing, whereby the whitening eflect thereof is weakened.

Various proposals have been made to avoid the above disadvantages of the prior art processes. For instance, there has been proposed a method in which a substituent capable of improving dyability is introduced into gelatin. For example, polyvinyl pyrrolidone (Japanese Pat. No. 7127(1959)) and poly-N-vinyl-5-methyl-3-oxazolidinone (Japanese Pat. No. 22,065 (1964) each being capable of being readily dyed by a fluorescent brightening agent, have been dispersed in an aqueous gelatin solution and then dyed by a fluorescent brightening agent. However, even by employing such methods, the diffusion of the fluorescent brightening agent employed has yet to be sufi'iciently prevented and the whitening effect of the agent is still considerably degraded during photographic processing and washing.

The inventors have previously found that as disclosed in their U.S. application Ser. No. 720,344, filed Apr. 10, 1968 now Pat. No. 3,556,081, the aforesaid disadvantages are overcome to the same extent by using, as the fluorescent brightening agent a compound having a repeating unit represented by one of the following general formulas:

l 1 n (II) wherein R and R each represents a hydrogen atom, an alkyl group having 1-8 carbon atoms, an aryl group having 6-12 carbon atoms, a hydroxyalkyl group having 2-4 carbon atoms, or a substituted derivative thereof, a sulfoalkyl group having 1-4 carbon atoms, or an alkali metal salt or ammonium salt thereof; R represents a halogen atom, OR, SR,

wherein R and R each represents a hydrogen atom, an alkyl group having 1-12 carbon atoms, a hydroxyalkyl group having 1-12 carbon atoms, a sulfoalkyl group (or an alkali metal salt or an ammonium salt thereof) a carboxyalkyl group (or an alkali metal salt or an ammonium salt thereof), or an alkyl group, an aryl group having 6-18 carbon atoms, a hydroxy-, carboxyor sulfonic acidderivative thereof, or an alkali metal salt or an ammonium salt thereof, a cycloalkyl group having 2-10 carbon atoms, or a substituted cycloalkyl group; and wherein A represents an alkylene group having 4-5 carbon atoms or an alkylene group containing a heterocyclic atom or a heterocyclic atomic group; Y represents an alkylene group having 2-10 carbon atoms, a substituted alkylene group having 2-10 carbon atoms, an allylene group having 6-18 carbon atoms or a substituted allylene group having 6-18 carbon atoms; Z represents a divalent heterocyclic atom or atomic group; M represents an alkali metal atom or NH X represents OH, Cl or NH m is 0 or 1 and n is to 120. That is, the fluorescent brightening agent is less difiused out during photographic processing or washing when incorporated in a photographic emulsion layer or a supplemental layer. Further, it has been found that this is resistant to staining when exposed to ultraviolet rays. Furthermore, these fluorescent brightening agents have been found to be excellent in fluorescent intensity and wave length.

It is also known to incorporate an ultraviolet absorbent in the photographic emulsion layer or an upper layer applied on that photographic emulsion layer for improving the fade-resistance of color images. The known ultraviolet absorbents are those absorbing ultraviolet rays having wave lengths of 300-400 me. It is also known that a ultraviolet absorbent capable of absorbing ultraviolet rays having wave lengths as long as possible is more effectively employed.

However, when the absorption edge of known ultraviolet absorbents extends across 400 me, the ultraviolet absorbent becomes yellow in color, and thus influences adversely the whiteness of the printing paper.

It is therefore, an object of this invention to provide a color photographic printing paper wherein the above coloration, resulting from the use of an ultraviolent absorbent, is substantially avoided.

It is a further object of this invention to provide a color photographic printing paper which has been whitened by a fluorescent brightening agent, wherein fading of the color upon exposure to light is reduced by the addition of an ultraviolet absorbent, without adversely affecting the whiteness thereof.

A further object of this invention is the provision of a color photographic printing paper containing an ultraviolet absorbent and a fluorescent whitening agent which is not subject to the aforesaid disadvantages.

The aforesaid objects of the present invention can be achieved by incorporating a fluorescent brightening agent having at least one repeating unit represented by the general Formula I or II in at least one photographic layer of a color photographic printing paper, said layer containing an ultraviolet absorbent, and photographic layers 4 present at the side of said photographic layer containing the ultraviolet absorbent and opposite to the support side of the paper.

For example, in one embodiment of a color photographic printing paper, there are provided on a support, a baryta layer, a blue-sensitive emulsion layer containing a yellow coupler, an intermediate layer, a green-sensitive emulsion layer containing a magenta coupler, an intermediate layer, a red-sensitive emulsion layer containing a cyan coupler, and a protective layer in that order. The ultraviolet absorbent is incorporated in the intermediate layer between the cyan couplercontaining emulsion layer and the magenta coupler-containing emulsion layer and the fluorescent brightening agent is incorporated in the protective layer.

The fluorescent brightening agent used in the present invention is a high molecular weight compound having the repeating unit of the general Formula I or II as mentioned above. The ultraviolet absorbent used in this invention may be, for instance,

(1) A benzotriazole derivative represented by the following general formula:

(III) wherein R R and R each represents a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an aromatic group, or a heterocyclic ring;

(2) A benzophenone derivative represented by general Formula IV I R2" OH wherein R" represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group; R represents an aryl group or a pyridyl group; and Q represents an imino group, a thiazole derivative, a cinnamic acid ester derivative, an oxazole derivative, an imidazole derivative, an oxadiazole derivative, thiadiazole derivative, a thiophene, benzalazine derivative, or a bishydroxyarylamide compound.

The ultraviolet absorbent may be incorporated in the coating composition for photographic layer as (1) an emulsified dispersion in an aqueous gelatin solution, (2) a solution thereof in a high boiling solvent or a mixed solvent containing a high boiling solvent and a low boiling solvent or (3) an aqueous alkaline solution thereof.

The high molecular weight fluorescent brightening agents employed in the present invention and methods of preparing them are described completely in copending US. application Ser. No. 720,344, filed Apr. 10, 1968.

As set forth therein, the high molecular Weight compounds having the repeating unit represented by aforesaid general Formula I or II are generally prepared by dissolving or dispersing in a solvent, such as water or dimethylformamide, one mol of an S-triazine-stilbene derivative having the general formula R1 in (III) wherein X represents a halogen atom or an alkoxy group having 1-4 carbon atoms and R R and M are as indicated above, and about one mol of a diamino compound represented by general Formula IV or V as follows:

ELY-13 (III) Illa Illa HNY-(Z)m-YNH (V) wherein R Y, Z, and m are as indicated above, reacting this mixture at a temperature of from about 50 to 150 C. with the addition of 2-2.4 mols of an aqueous sodium hydroxide solution. In addition high molecular weight compounds of this invention may be prepared by other methods and may be employed in this invention.

The bis-S-triazine-stilbene derivative described by general Formula III may be prepared by conventional methods, as shown in The Journal of the Society of Organic Chemistry, Japan, vol. 20, 64 (1962).

For example, the derivative may be prepared by reacting 2 mols of cyanuric chloride with one mole .of a derivative of 4,4'-diaminostilbene-2,2-disulfonate represented by the general formula l wherein R and M are as set forth above, at a temperature of about C. to C. The compound thus obtained is reacted with 2 mols of a nucleophilic agent illustrated by the formula HR wherein R is as set forth above, at a temperature of from about 0 to 20 C.

Some examples of R R, Y, and Z' in the repeating unit (I) or (H) of the high molecular weight compound of this invention are as follows: R and R may be, for example: H, -CH 2 5 3 T, 2 a)2 -CH CH OH, -CH CH CH OH, CH CH 0CH CH CH OCH --CH -SO M' (where M represents H, Na, K or NH (CH SO M, -(CH SO M', and the like.

R may be for example:

COOM

sonvr' on 503M, COOM' 30 (where M=H, Na, K or NH and P=1, 2, 3 or 4 As examples of Y may be mentioned:

(Where M'=H, Na, K or NH Z may be exemplified QCH=CH- by O, S, and S0 Typical examples of compounds included in general 03M a Formulas I or II which may be used in this invention 5 are as follows:

SOaNH4 N N SOaNHa It will, of course, be understood, that the number of repeating units (represented by n) set forth in the foregoing examples may vary to some extent, the narration in some instances being up to about :20 repeating units.

These compounds may generally be prepared by the methods described above, but an example will be given in detail for Compound 1.

A solution of 14.7 parts by weight of cyanuric chloride in 80 parts of acetone is dispersed in a slurry of 240 parts by Weight of ice water, and the dispersion is maintained at about 0-3 C. To the dispersion there is added dropwise 16.5 parts of sodium 4,4'-diaminostilbene-2,2'-disulfonate as a aqueous solution. During the addition, hydrochloric acid is formed in the system, and an aqueous solution of sodium carbonate is added dropwise (4.2 parts by weight sodium carbonate and 50 parts by weight water) so that the pH of the system is in the range of 4-5. The system is, thereafter, stirred for about 30 minutes at about 0-5 0., and 7.5 parts of aniline is further added to the reaction mixture. Thereafter, the temperature of the system is increased to 20 C. and an aqueous solution of sodium carbonate (4.2 parts by weight sodium carbonate and 60 parts by weight water) is added gradually to the system.

After conducting the reaction for about 3 hours at the same temperature, 2.4 parts by weight of ethylenediamine is added to the reaction mixture, and the reaction temperature is increased to 100 C. The reaction mixture is stirred for 2 hours at 100 C. Upon filtering the reaction mixture after cooling, Compound 1 is obtained.

The compound thus obtained is soluble in a dimethylformamide-water 1:1 solvent, and the intrinsic viscosity of the compound in the same solvent is 0.32 at 30.0 C.

Likewise, typical examples of ultraviolet absorbents. which may be used in the present invention are as follows:

CAHB (t) o dnzomon Proportions of high molecular weight fluoroscent'brightening agent which may be employed in the printing papers brightening agent of this invention range from 05-10 mg./ 100 cm. and those of the ultraviolet absorbent range from 2-20 mg./100 cm. v p

Almost all conventionally known fluorescent brightening agents are simultaneously ultraviolet absorbents. The fluorescent brightening agent may be added to the system by either the direct or the'indirect method as set forth above. I i

When known fluorescent brightening agents are added to an uppermost layer of a photographic light sensitive color printing paper by the indirect method,-that1ayer frequently becomes subject to damage by external impact or friction. vFurther, the layer may become sticky, particularly when mounted in an album as a result of solvent action. Therefore, when such conventional fluorescent brightening agents are employed, they must be incorporated in a photographic layer other than the uppermost layer.

However, when the fluorescent brightening agents of this invention are employed, it is possible to incorporate them in the uppermost layer without incurring such disadvantages. Hence the fluorescent brightening agents of this invention may be incorporated in the uppermost layer to be effectively utilized as an ultraviolet absorbent.

, Of course, it will be understood that the high molecular weight compound of this invention may be incorporatedin any layer to effect ultraviolet preventing and fluorescent brightening action.

The term photographic emulsion in this application is defined to mean the usual gelatino silver halide light sensitive emulsions, but synthetic resins such as polyvinyl alcohol and polyvinyl acetate may be effectively employed as protective colloids for the photographic emulsion, in addition to gelatin, in this invention. I

In the present invention, the order ofthe photographic layers, as well as the number of the layers, may be varied as is well known in the art. Moreover, the "ultraviolet absorbent of this invention may be incorporated in any layer except the protective, or uppermostlayei'. Further,

the fluorescent brightening agents of this invention may be agent of this invention was incorporated in the uppermost incorporated either in the layer containing the ultraviolet layer, the use of a whitening procedure for the baryta absorbent or in a layer positioned at the side of the ultralayer was unnecessary.

violet absorbent-containing layer opposite to the side of EXAMPLE 2 support. To a bar a-coated a er was a lied a blue-sensitive mventlon {my be lnuitrated i the fOHPWIiIg typl' silver iodob i omide em ul ion conta i r l ing 3,5-dicarboxy-acal examples whlch .exemphfy vanous fombmatlons of (4-stearoylamidobenzoyl) acetanilide as a yellow coupler.

the water'soluble hlgh molecular welght fluorescent The coupler was added as an aqueous alkaline solution brightening agent and the ultraviolet absorbent, although the reof. Thereafter a ecu-sensitive silver chlorobromrde t will be understood that the rnventlon shall not be 11memulsion containing f (3 sulfo 4 phenoxy) 3 stearoy1 5 thereby pyrazolone as a magenta coupler was applied to the blue- EXAMPLE 1 sensitive layer. An ultraviolet absorbent, one of the Com- Compound 1, supra, was employed as the high molecular PP -23, Supra, Was {lispersed y emulsification in weight fluorescent brightening agent, and the effect thereof flf P f and the fllspersion Was added to a Was measured A color photographic paper con. sensltlve Sliver Chlorobl'omlde emulsion togther N- sisting of a support, a baryta paper, a blue-sensitive emul- Y Y- 'P p as y sion layer containing 3,5-dicarboxy-a-(4-stearoylamidop f f he resultmg emulsron was applied to the benzoyl) acetanilide as the yellow coupler, an intermediate green'sensltlve emulslon f y fills y there was layer, a green-sensitive emulsion layer containing 1,3-sulfofufther formed a protFctlve layfir 111 a thlckness 0f 4 phenoxyphenyl) 3 stearoyl 5 pyrazolone as the magenta mrcrons. ThlS protective layer was formed by adding coupler, an ultraviolet absorption layer containing Com- Slowly a 4% dlmethyl fofmamlde-wfltel Solution of 0116 pound 17, supra, as the ultraviolet absorbent, a red-sensiof the compoflnds 1714, Supra, as a g molecular W g tive emulsion layer containing N-n-octadecyl-1-hydroxy-4- fluorescent brlghtenlng agent Compound 24 sulfo-Z-naphthamide as the cyan coupler, and a protective 25 mg the P f9rmlllas as Shown below, well known layer, in this order, was prepared and designated 1 fluorescent bnghtenlng agent, to an aqueous gelatm soluphotographic printing paper addition, a photo tron and applying the resulting mixture in a thickness of graphic color printing paper having the same photographic 5 lug/100 followed y y layers as above in the same order, but containing no ultra- The color photographic printing paper thus prepared violet absorbent in the intermediate layer between the was developed in a developer containing N-ethyl-N-B- green-sensitive emulsion layer and the red-sensitive emulhydroxyethyl-p-phenylenediamine and thereafter subjected sion layer was prepared, and is designated color phototo stop fixing, washing, bleach fixing, washing, hardening, graphic printing paper B. Compound 1 was incorporated washing, and drying. The whiteness of the printing paper in each layer of the photographic color printing paper A thus processed is shown in the following table.

and photographic color printing paper B at a level of 5 mg./ 100 cm, and the thus prepared color photographic DENSITY OF YELLOW COMIII"I(C))IENT OF UNEXPOSED POR- processing. The whiteness of the color photographic printing papers thus processed is shown in the following table, in which the whiteness is shown by photographic density fluorescent Compound brightening of the yellow component 1n the unexposed portions of the agent 15 16 17 18 19 20 processed printing papers.

&

DENSITY or YELLOW COMPONENT IN UNEXPOSED POR- 3:8,; 218% 3:8; 33; 3:8; TION 8'88 8'88 8'83 8'88 883 8'8? 8? 83 0. 0. Printing Paper 0. 06 0.06 0.07 0.06 0.07 0.07 0.07 0.07 Layertowhichcomvoundisadded A B 8:88 8:88 8:8? 8:88 8:8? 8:83 883 8:83 0.06 0.06 0.07 0.06 0.07 0.07 0.07 0.07 gg g g g-gg 0.06 0. 06 0. 07 0.06 0.07 0.07 0.07 0.07 Y 0.06 0.06 0.07 0.06 0.07 0.07 0.07 0.07 Ultravioletabsorbinglayer(ormtermed1ate1ayer) 0 10 0.08 0.06 Q06 0'07 0'06 (107 0.07 Q07 0.07

8-83 0.06 0.06 0.07 0.06 0. 07 0.07 0.07 0.07 yanowela M Y 0.06 0. 06 0.07 0.06 0.07 0. 07 0. 07 0.07 Ba v dog 0.06 0.06 0.07 0.06 0.07 0.07 0.07 0.07 g z 0.11 0.11 0.12 0.11 0.12 0.12 0.12 0.12 e 0.11 0.11 0.12 0.11 0.12 0.12 0.12 0.12 0.12 0.12 0.13 0.12 0.13 0.13 0.13 0.13

From the above results, it can be seen that the effect of the fluorescent brightening agent was most remarkable when it was incorporated in the uppermost layer, and that As can be clearly seen from the above results, when a the eifect became less as it was incorporated in those high molecular fluorescent brightening agent of this inlayers nearer the support. Also, it should be noted that, vention was incorporated in the uppermost layer of the when the high-molecular weight fluorescent brightening color photographic printing paper, a very remarkable Ra Ra N N X-- TN CH=CH N( l N N 5503M sonu N l R1 R1 and N X-- I N R I o N N N SOaM SOaM I I R1 R1 wherein 1R and R are each a member selected from the group consisting of a hydrogen atom, an alkyl group having 1-8 carbon atoms, an aryl group having '6-12 carbon atoms, a hydroxyalkyl group having 2-4 carbon atoms, a substituted hydroxy alkyl group having 2-4 carbon atoms, a sulfoalkyl group having 1-4 carbon atoms, and alkali metal salts and ammonium salts thereof; R is a member selected from the group consisting of a halogen atom, 0R, S

and

wherein R and R are each a member selected from the group consisting of a hydrogen atom, an alkyl group having 1-12 carbon atoms, a hydroxyalkyl group having 1-12 carbon atoms, a sulfoalkyl group, an alkali metal salt of said sulfoalkyl group, an ammonium salt of said sulfoal kyl group, a carboxyalkyl group, an alkali metal salt of said carboxyalkyl group, an ammonium salt of said carboxyalkyl group, an alkyl group, an aryl group having 6-18 carbon atoms, a hydroxyl derivative of said aryl group, a carboxyl derivative of said aryl group, a sulfonic acid derivative of said aryl group, an alkali metal salt of each said derivative, an ammonium salt of such said derivative, a cycloalkyl group havingZ-IO carbon 1 35 atoms, and a substituted cycloalkyl group; A is a member selected from the group consisting of an alkylene group having 4-5 carbon atoms, an alkylene group containing a heterocyclic atom, and an alkylene group containing a heterocyclic atomic group; Y is a member selected from the group consisting of an alkylene group having 2-10 carbon atoms, a substituted alkylene group having 2-1() carbon atoms, an allylene group having 6-18 carbon atoms and a substituted allylene group having 6-18 carbon atoms, Z is a member selected from the group consisting of a divalent heterocyclic atom and a divalent heterocyclic atomic group; M is a member selected from the group consisting of an alkali metal atom and NIL; X is a member selected from the group consisting of hydroxyl, chloro and amino; m is O or 1, and n is 5 to 120.

2. The color photographic printing paper as claimed in claim 1 wherein said ultraviolet absorbent is a member selected from the group consisting of a benzotriazole, a benozophenone and a thiazolidone.

3. The color photographic printing paper as recited in claim 2 wherein the amount of said compound is 05-10 mg./ cm. and the amount of said ultraviolet absorbent is 2-20 mg./ 100 cm.

4. The color photographic printing paper as recited in claim 1 wherein said printing paper comprises a layer containing said ultraviolet absorbent and a layer containing said compound, the layer containing said ultraviolet absorbent being positioned between said compound-containing layer and said support paper.

5. The color photographic printing paper as recited in claim 4, wherein said compound is incorporated in the uppermost protective layer of the printing paper.

6. The color photographic printing paper as recited in claim 1 wherein said ultraviolet absorbent and said compound are both present in a single layer.

7. The color photographic printing paper as recited in claim 1 wherein said ultraviolet absorbent is incorporated in a layer below the uppermost layer.

8. The color photographic paper as recited in claim 6 wherein said ultraviolet absorbent and said compound are present in a layer beneath the uppermost layer.

9. The color photographic printing paper as claimed in claim 1 wherein said compound is selected from the group consisting of S0 Na SOaNa S O Na S 0 1%.

NORMAN G. TORCHIN, Primary Examiner E. C. KIMLIN, Assistant Examiner US. Cl. X.R. 96-48